TWI824089B - Biaxially oriented polypropylene film - Google Patents

Biaxially oriented polypropylene film Download PDF

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TWI824089B
TWI824089B TW108147639A TW108147639A TWI824089B TW I824089 B TWI824089 B TW I824089B TW 108147639 A TW108147639 A TW 108147639A TW 108147639 A TW108147639 A TW 108147639A TW I824089 B TWI824089 B TW I824089B
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film
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polypropylene film
width direction
biaxially aligned
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TW202031752A (en
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山田浩司
堀之内一仁
中野麻洋
今井徹
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日商東洋紡股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00Producing flat articles, e.g. films or sheets
    • B29D7/01Films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10Polymers of propylene
    • B29K2023/12PP, i.e. polypropylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/005Oriented
    • B29K2995/0053Oriented bi-axially
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10Homopolymers or copolymers of propene
    • C08J2323/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10Homopolymers or copolymers of propene
    • C08J2423/12Polypropene

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

本發明之課題在於提供一種雙軸配向聚丙烯膜,該雙軸配向聚丙烯膜的剛性高,在達150℃的高溫的耐熱性仍優異,易於保持作為包裝袋時的袋狀,而且印刷時的間距偏差和經熱封時密封部的皺褶少。 本發明為一種雙軸配向聚丙烯膜,該雙軸配向聚丙烯膜係以熱機械分析裝置(TMA)所測定於150℃以下的最大伸長量在長度方向為1.5mm以下,在寬度方向為0.1mm以下,且於150℃中的熱收縮率在長度方向為10%以下,在寬度方向為30%以下。An object of the present invention is to provide a biaxially aligned polypropylene film that has high rigidity, excellent heat resistance at high temperatures up to 150° C., is easy to maintain the bag shape when used as a packaging bag, and can be printed There is less spacing deviation and less wrinkles in the sealing part during heat sealing. The present invention is a biaxially aligned polypropylene film. The maximum elongation of the biaxially aligned polypropylene film measured below 150°C by a thermomechanical analysis device (TMA) is 1.5 mm or less in the length direction and 0.1 in the width direction. mm or less, and the thermal shrinkage rate at 150°C is 10% or less in the length direction and 30% or less in the width direction.

Description

雙軸配向聚丙烯膜Biaxially oriented polypropylene film

本發明是關於一種剛性與耐熱性優異的雙軸配向聚丙烯膜。詳細而言,是關於一種雙軸配向聚丙烯膜,該雙軸配向聚丙烯膜由於易於保持作為包裝袋時的袋狀,而且經熱封時密封部的皺褶少,故能夠適合用於包裝袋。The present invention relates to a biaxially aligned polypropylene film with excellent rigidity and heat resistance. Specifically, it relates to a biaxially oriented polypropylene film that is suitable for packaging because it is easy to maintain the bag shape when used as a packaging bag and has few wrinkles in the sealing portion when heat-sealed. bag.

雙軸配向聚丙烯膜由於具有防濕性,而且具有所需的剛性、耐熱性,因此被用於包裝用途和工業用途。近年,隨著所使用的用途擴展,而尋求更高性能化,尤其是期待剛性的提升。再者,出於對環境的關懷,也尋求著即使減容(使膜厚度變薄)仍維持強度,然而因為如此,顯著地提昇剛性是不可欠缺的。作為提昇剛性的手段,已知藉由改良聚丙烯樹脂在聚合時的觸媒和製程技術會提昇該聚丙烯樹脂的結晶性和熔點,然而儘管有如此的改善,但是至今仍沒有具有充分的剛性的雙軸配向聚丙烯膜。Biaxially oriented polypropylene films are used in packaging and industrial applications because they are moisture-proof and have the required rigidity and heat resistance. In recent years, as the uses have expanded, higher performance has been sought, and in particular, improvements in rigidity have been expected. Furthermore, out of concern for the environment, it is also necessary to maintain strength even if the volume is reduced (thinner film thickness). However, because of this, it is indispensable to significantly improve the rigidity. As a means to improve rigidity, it is known that improving the catalyst and process technology during polymerization of polypropylene resin will increase the crystallinity and melting point of the polypropylene resin. However, despite such improvements, it still does not have sufficient rigidity so far. biaxially aligned polypropylene film.

目前已提出:在雙軸配向聚丙烯膜的製造步驟中,在朝寬度方向延伸後,一邊以寬度方向延伸時的溫度以下將膜弛緩一邊進行第一段的熱處理,在第二段以第一段溫度至寬度方向延伸溫度來進行熱處理之方法(例如,參照專利文獻1等);或在寬度方向延伸後,進一步朝長度方向進行延伸之方法(例如,參照專利文獻2等)。然而,專利文獻2所記載的膜雖然剛性優異,但熱封後容易在密封部產生皺褶,耐熱性差。又,專利文獻1記載的膜的配向低,剛性並不充分。 [先前技術文獻] [專利文獻]It has been proposed that in the manufacturing process of a biaxially aligned polypropylene film, after extending in the width direction, the first stage of heat treatment is performed while relaxing the film at a temperature below the temperature when extending in the width direction, and the first stage of heat treatment is performed in the second stage. A method of performing heat treatment from a segment temperature to a width direction stretching temperature (for example, refer to Patent Document 1, etc.); or a method of extending in the width direction and then further extending in the length direction (for example, refer to Patent Document 2, etc.). However, although the film described in Patent Document 2 has excellent rigidity, it is prone to wrinkles in the sealing portion after heat sealing and has poor heat resistance. In addition, the film described in Patent Document 1 has low orientation and insufficient rigidity. [Prior technical literature] [Patent Document]

[專利文獻1]WO2016/182003號國際公報。 [專利文獻2]日本特開2013-177645號公報。[Patent Document 1] International Publication No. WO2016/182003. [Patent Document 2] Japanese Patent Application Publication No. 2013-177645.

[發明所欲解決之課題][Problem to be solved by the invention]

本發明的課題在於解決上述的問題點。亦即,本發明係關於一種膜的剛性與在達150℃的高溫的耐熱性優異的雙軸配向聚丙烯膜。詳細而言,本發明係在於提供一種雙軸配向聚丙烯膜,該雙軸配向聚丙烯膜易於保持作為包裝袋時的袋狀,而且在經熱封時密封部及密封部的周圍少有皺褶。 [用以解決課題之手段]An object of the present invention is to solve the above-mentioned problems. That is, the present invention relates to a biaxially oriented polypropylene film which is excellent in film rigidity and heat resistance at high temperatures up to 150°C. Specifically, the present invention is to provide a biaxially aligned polypropylene film that is easy to maintain the bag shape when used as a packaging bag and has few wrinkles at the sealing portion and the periphery of the sealing portion when heat-sealed. pleats. [Means used to solve problems]

本案發明人等為了達成該目的而深入探討的結果,發現若雙軸配向聚丙烯膜以熱機械分析裝置(TMA;Thermomechanical Analyzer)所測定於150℃以下的最大伸長量在長度方向為1.5mm以下,在寬度方向為0.1mm以下,且於150℃中的熱收縮率在長度方向為10%以下,在寬度方向為30%以下,能夠獲得膜的加工性與在達150℃的高溫的耐熱性優異之雙軸配向聚丙烯膜。As a result of in-depth research by the inventors of the present case to achieve this goal, they found that if the maximum elongation of the biaxially aligned polypropylene film at 150°C or less measured by a thermomechanical analyzer (TMA; Thermomechanical Analyzer) is 1.5 mm or less in the length direction , in the width direction is 0.1mm or less, and the thermal shrinkage rate at 150°C is 10% or less in the length direction, and 30% or less in the width direction, it is possible to obtain film processability and heat resistance at high temperatures up to 150°C. Excellent biaxially aligned polypropylene film.

在這種情況中,較合適的是前述雙軸配向聚丙烯膜於120℃中的熱收縮率在長度方向為2.0%以下,在寬度方向為5.0%以下,且長度方向的120℃熱收縮率小於寬度方向的120℃熱收縮率。In this case, it is more suitable that the thermal shrinkage rate of the aforementioned biaxially aligned polypropylene film at 120°C is 2.0% or less in the length direction and 5.0% or less in the width direction, and the 120°C thermal shrinkage rate in the length direction is Less than the 120°C thermal shrinkage in the width direction.

又,在這種情況中,較合適的是前述雙軸配向聚丙烯膜的長度方向之折射率Ny為1.5230以上,ΔNy為0.0220以上。In this case, it is more suitable that the refractive index Ny of the biaxially aligned polypropylene film in the longitudinal direction is 1.5230 or more, and ΔNy is 0.0220 or more.

進而,在這種情況中,較合適的是前述雙軸配向聚丙烯膜的霧度為5.0%以下。Furthermore, in this case, it is more suitable that the haze of the biaxially aligned polypropylene film is 5.0% or less.

進而,在這種情況中,較合適的是構成前述雙軸配向聚丙烯膜的聚丙烯樹脂之內消旋五單元組分率為97.0%以上。Furthermore, in this case, it is more suitable that the racemic pentad component ratio of the polypropylene resin constituting the biaxially aligned polypropylene film is 97.0% or more.

進而,在這種情況中,較合適的是構成前述雙軸配向聚丙烯膜的聚丙烯樹脂之結晶化溫度為105℃以上,熔點為160℃以上。Furthermore, in this case, it is more suitable that the polypropylene resin constituting the biaxially aligned polypropylene film has a crystallization temperature of 105°C or higher and a melting point of 160°C or higher.

進而,在這種情況中,較合適的是構成前述雙軸配向聚丙烯膜的聚丙烯樹脂之熔體流動速率為4.0g/10分鐘以上。Furthermore, in this case, it is more suitable that the melt flow rate of the polypropylene resin constituting the biaxially aligned polypropylene film is 4.0 g/10 minutes or more.

進而,在這種情況中,較合適的是構成前述雙軸配向聚丙烯膜的聚丙烯樹脂之分子量10萬以下的成分量為35質量%以上。Furthermore, in this case, it is more suitable that the component amount of the polypropylene resin constituting the biaxially aligned polypropylene film with a molecular weight of 100,000 or less is 35 mass % or more.

進而,在這種情況中,較合適的是前述雙軸配向聚丙烯膜的配向度為0.85以上。 [發明功效]Furthermore, in this case, it is more suitable that the orientation degree of the biaxially aligned polypropylene film is 0.85 or more. [Invention effect]

本發明之雙軸配向聚丙烯膜,由於剛性高,在達150℃的高溫的耐熱性亦優異,因此易於保持作為包裝袋時的袋狀,而且由於在經熱封時密封部的皺褶少,因此能夠獲得可適合用於包裝袋的雙軸配向聚丙烯膜。又,因為該雙軸配向聚丙烯膜剛性也優異,即使將膜的厚度變薄仍能夠維持強度,而且亦能夠適合用於需要更高剛性的用途。The biaxially aligned polypropylene film of the present invention has high rigidity and excellent heat resistance at high temperatures up to 150° C., so it is easy to maintain the bag shape when used as a packaging bag, and has fewer wrinkles in the sealing portion when heat-sealed. , therefore a biaxially oriented polypropylene film suitable for packaging bags can be obtained. In addition, since the biaxially aligned polypropylene film also has excellent rigidity, it can maintain its strength even if the thickness of the film is reduced, and can also be suitably used for applications requiring higher rigidity.

以下,針對本發明之雙軸配向聚丙烯膜進一步詳細地說明。 本發明之雙軸配向聚丙烯膜是由將聚丙烯樹脂作為主成分的聚丙烯樹脂組成物所構成。另外,所謂的「主成分」,意思是聚丙烯樹脂在聚丙烯樹脂組成物中所佔的比例為90質量%以上、更佳為93質量%以上、進而較佳為95質量%以上、特佳為97質量%以上。Hereinafter, the biaxially aligned polypropylene film of the present invention will be described in further detail. The biaxially aligned polypropylene film of the present invention is composed of a polypropylene resin composition containing polypropylene resin as a main component. In addition, the so-called "main component" means that the proportion of the polypropylene resin in the polypropylene resin composition is 90 mass% or more, more preferably 93 mass% or more, still more preferably 95 mass% or more, and particularly preferably It is more than 97% by mass.

[聚丙烯樹脂] 本發明所使用的聚丙烯樹脂,能夠使用聚丙烯同元聚合物、和聚丙烯與乙烯及/或碳數4以上之α-烯烴的共聚物。較佳為實質上不含乙烯及/或碳數4以上之α-烯烴的丙烯同元聚合物,即使是包含乙烯及/或碳數4以上之α-烯烴成分的情況,較佳為乙烯及/或碳數4以上之α-烯烴成分量為1莫耳%以下。成分量的上限更佳為0.5莫耳%、進而較佳為0.3莫耳%、特佳為0.1莫耳%。若為上述範圍則結晶性易於提升。作為構成這種共聚物的碳數4以上之α-烯烴成分,例如可列舉出:1-丁烯、1-戊烯、3-甲基戊烯-1、3-甲基丁烯-1、1-己烯、4-甲基戊烯-1、5-乙基己烯-1、1-辛烯、1-癸烯、1-十二烯、1-十四烯、1-十六烯、1-十七烯、1-十八烯、1-二十烯等。 聚丙烯樹脂能夠使用不同的2種以上之聚丙烯同元聚合物、聚丙烯與乙烯及/或碳數4以上之α-烯烴的共聚物、及該等的混合物。[Polypropylene resin] As the polypropylene resin used in the present invention, polypropylene homopolymers and copolymers of polypropylene, ethylene and/or α-olefin having 4 or more carbon atoms can be used. Preferably, it is a propylene homopolymer that does not substantially contain ethylene and/or α-olefins with 4 or more carbon atoms. Even if it contains ethylene and/or α-olefin components with 4 or more carbon atoms, it is preferably ethylene and /or the content of the α-olefin component having 4 or more carbon atoms is 1 mol% or less. The upper limit of the component amount is more preferably 0.5 mol%, still more preferably 0.3 mol%, and particularly preferably 0.1 mol%. If it is within the above range, the crystallinity will be easily improved. Examples of the α-olefin component having 4 or more carbon atoms constituting the copolymer include 1-butene, 1-pentene, 3-methylpentene-1, 3-methylbutene-1, 1-hexene, 4-methylpentene-1, 5-ethylhexene-1, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene , 1-heptadecene, 1-octadecene, 1-eicosene, etc. As the polypropylene resin, two or more different polypropylene homopolymers, copolymers of polypropylene and ethylene and/or α-olefin having 4 or more carbon atoms, and mixtures thereof can be used.

[立體規則性] 作為本發明所使用的聚丙烯樹脂的立體規則性之指標的內消旋五單元組分率([mmmm]%),較佳為97.0%至99.9%的範圍內、更佳為97.5%至99.7%的範圍內、進而較佳為98.0%至99.5%的範圍內、特佳為98.5%至99.3%的範圍內。 若為97.0%以上,聚丙烯樹脂的結晶性會提高,膜之中的結晶的熔點、結晶度、結晶配向度會提升,易於獲得剛性與在高溫的耐熱性。若為99.9%以下則在聚丙烯製造這一點易於抑制成本,在製膜時則變得不易斷裂。更佳為99.5%以下。內消旋五單元組分率是以核磁共振法(所謂NMR法)來測定。 為了將聚丙烯樹脂的內消旋五單元組分率設在上述的範圍內,較佳可採用將獲得的聚丙烯樹脂粉末以正庚烷等的溶劑來洗淨之方法、或適當進行觸媒及/或輔觸媒的選定、聚丙烯樹脂組成物之成分的選定之方法等。[Three-dimensional regularity] The meso pentad ratio ([mmmm]%), which is an index of the stereoregularity of the polypropylene resin used in the present invention, is preferably in the range of 97.0% to 99.9%, more preferably 97.5% to 99.7 %, more preferably within the range of 98.0% to 99.5%, particularly preferably within the range of 98.5% to 99.3%. If it is 97.0% or more, the crystallinity of the polypropylene resin will increase, and the melting point, crystallinity, and crystal orientation of the crystals in the film will increase, making it easier to obtain rigidity and heat resistance at high temperatures. If it is 99.9% or less, it will be easier to suppress costs in terms of polypropylene production, and it will be less likely to break during film production. More preferably, it is 99.5% or less. The meso pentad ratio is measured by the nuclear magnetic resonance method (so-called NMR method). In order to set the meso pentad ratio of the polypropylene resin within the above range, it is preferable to use a method of washing the obtained polypropylene resin powder with a solvent such as n-heptane, or to catalyze it appropriately. And/or the selection of auxiliary catalysts, the method of selecting the components of the polypropylene resin composition, etc.

[熔化溫度] 構成本發明之雙軸配向聚丙烯膜的上述聚丙烯樹脂在DSC(Differential Scanning Calorimeter;差示掃描型熱量計)所測定的熔化溫度(Tm)的下限較佳為160℃、更佳為161℃、進而較佳為162℃、又更佳為163℃。若Tm為160℃以上則可易於獲得剛性與在高溫的耐熱性。 Tm的上限較佳為170℃、更佳為169℃、進而較佳為168℃、又更佳為167℃、特佳為166℃。若Tm為170℃以下,則在聚丙烯製造這一點可易於抑制成本上升,且在製膜時變得不易斷裂。藉由在前述的聚丙烯樹脂調配成核劑,能夠使熔化溫度更加提高。 所謂的Tm,是將1mg至10mg的樣品塞進鋁盤並安裝於差示掃描型熱量計(DSC),在氮氣氛圍下以230℃熔化5分鐘,以掃描速度-10℃/分鐘降溫至30℃後保持5分鐘,以掃描速度10℃/分鐘昇溫時所觀察到的伴隨熔化的吸熱峰之主要峰溫度。[melting temperature] The lower limit of the melting temperature (Tm) of the above-mentioned polypropylene resin constituting the biaxially aligned polypropylene film of the present invention as measured by DSC (Differential Scanning Calorimeter; differential scanning calorimeter) is preferably 160°C, more preferably 161°C. , more preferably 162°C, still more preferably 163°C. If Tm is 160°C or higher, rigidity and high temperature heat resistance can be easily obtained. The upper limit of Tm is preferably 170°C, more preferably 169°C, further preferably 168°C, still more preferably 167°C, and particularly preferably 166°C. If Tm is 170° C. or less, an increase in cost can be easily suppressed in the production of polypropylene, and it becomes less likely to break during film formation. By blending a nucleating agent with the aforementioned polypropylene resin, the melting temperature can be further increased. The so-called Tm is to put 1 mg to 10 mg of sample into an aluminum plate and install it on a differential scanning calorimeter (DSC). It is melted at 230°C for 5 minutes in a nitrogen atmosphere, and then cooled to 30 at a scanning speed of -10°C/min. The main peak temperature of the endothermic peak accompanying melting was observed when the temperature was raised for 5 minutes at a scanning speed of 10°C/min.

[結晶化溫度] 構成本發明之雙軸配向聚丙烯膜的上述聚丙烯樹脂在DSC所測定的結晶化溫度(Tc)的下限為105℃、較佳為108℃、更佳為110℃。若Tc為105℃以上,則在寬度方向延伸與隨後接續的冷卻步驟中結晶化易於進展,易於獲得剛性與在高溫的耐熱性。 Tc的上限較佳為135℃、更佳為133℃、進而較佳為132℃、又更佳為130℃、特佳為128℃、最佳為127℃。若Tc為135℃以下則在聚丙烯製造這一點成本不易上升,且在製膜時變得不易斷裂。 所謂的Tc,是將1mg至10mg的樣品塞進鋁盤並安裝於DSC,在氮氣氛圍下以230℃熔化5分鐘,以掃描速度-10℃/分鐘降溫至30℃時所觀察到的放熱峰之主要峰溫度。 藉由在前述的聚丙烯樹脂調配成核劑,亦能夠使結晶化溫度更加提高。[Crystallization temperature] The lower limit of the crystallization temperature (Tc) measured by DSC of the above-mentioned polypropylene resin constituting the biaxially aligned polypropylene film of the present invention is 105°C, preferably 108°C, and more preferably 110°C. If Tc is 105° C. or higher, crystallization is likely to progress in the width direction stretching and subsequent cooling steps, and rigidity and high-temperature heat resistance are easily obtained. The upper limit of Tc is preferably 135°C, more preferably 133°C, further preferably 132°C, still more preferably 130°C, particularly preferably 128°C, and most preferably 127°C. If Tc is 135° C. or less, the cost of polypropylene production is less likely to increase, and the polypropylene is less likely to break during film formation. The so-called Tc is one of the exothermic peaks observed when a sample of 1 mg to 10 mg is stuffed into an aluminum pan and mounted on a DSC, melted at 230°C for 5 minutes in a nitrogen atmosphere, and cooled to 30°C at a scanning speed of -10°C/min. Main peak temperature. By blending a nucleating agent into the aforementioned polypropylene resin, the crystallization temperature can be further increased.

[熔體流動速率] 構成本發明之雙軸配向聚丙烯膜的上述聚丙烯樹脂的熔體流動速率(MFR),在遵循JIS K 7210(1995)的條件M(230℃,2.16kgf)來測定的情況中,較佳為4.0g/10分鐘至30g/10分鐘、更佳為4.5g/10分鐘至25g/10分鐘、進而較佳為4.8g/10分鐘至22g/10分鐘、特佳為5.0g/10分鐘至20g/10分鐘、最佳為6.0g/10分鐘至20g/10分鐘。 若聚丙烯樹脂的熔體流動速率(MFR)為4.0g/10分鐘以上,則易於獲得熱收縮低的雙軸配向聚丙烯膜。 再者,若聚丙烯樹脂的熔體流動速率(MFR)為30g/10分鐘以下,則易於維持膜的製膜性。[Melt flow rate] The melt flow rate (MFR) of the polypropylene resin constituting the biaxially aligned polypropylene film of the present invention is preferably measured in accordance with the conditions M (230°C, 2.16kgf) of JIS K 7210 (1995). It is 4.0g/10 minutes to 30g/10 minutes, more preferably 4.5g/10 minutes to 25g/10 minutes, further preferably 4.8g/10 minutes to 22g/10 minutes, particularly preferably 5.0g/10 minutes to 20g/10 minutes, optimally 6.0g/10 minutes to 20g/10 minutes. If the melt flow rate (MFR) of the polypropylene resin is 4.0 g/10 minutes or more, a biaxially aligned polypropylene film with low thermal shrinkage can be easily obtained. Furthermore, when the melt flow rate (MFR) of the polypropylene resin is 30 g/10 minutes or less, the film forming properties of the film can be easily maintained.

從膜特性的觀點而言,宜將構成膜之聚丙烯樹脂的熔體流動速率(MFR)(230℃,2.16kgf)的下限設在較佳為5.0g/10分鐘、更佳為5.5g/10分鐘、進而較佳為6.0g/10分鐘、特佳為6.3g/10分鐘、最佳為6.5g/10分鐘。 若聚丙烯樹脂的熔體流動速率(MFR)為5.0g/10分鐘以上,則由於構成膜之聚丙烯樹脂的低分子量成分量變多,因此藉由採用在後述的膜製膜步驟之寬度方向延伸步驟,會更加促進聚丙烯樹脂的配向結晶化,及膜中的結晶度變得易於更加提高,再加上非晶部分的聚丙烯分子鏈彼此的纏繞會變得更少,更容易提高耐熱性。 為了將聚丙烯樹脂的熔體流動速率(MFR)設在上述的範圍內,較佳為採用控制聚丙烯樹脂的平均分子量和分子量分布之方法等。From the viewpoint of film properties, it is preferable to set the lower limit of the melt flow rate (MFR) (230°C, 2.16kgf) of the polypropylene resin constituting the film to preferably 5.0g/10 minutes, more preferably 5.5g/ 10 minutes, more preferably 6.0g/10 minutes, particularly preferably 6.3g/10 minutes, most preferably 6.5g/10 minutes. If the melt flow rate (MFR) of the polypropylene resin is 5.0 g/10 minutes or more, the amount of low molecular weight components of the polypropylene resin constituting the film increases. Therefore, by using the width direction stretching in the film forming step described below, This step will further promote the alignment crystallization of the polypropylene resin, and the crystallinity in the film will become easier to increase. In addition, the polypropylene molecular chains in the amorphous part will become less entangled with each other, making it easier to improve the heat resistance. . In order to set the melt flow rate (MFR) of the polypropylene resin within the above range, it is preferable to use a method of controlling the average molecular weight and molecular weight distribution of the polypropylene resin.

亦即,本發明之構成膜之聚丙烯樹脂的GPC(Gel Permeation Chromatography;凝膠滲透層析法)累積曲線中的分子量10萬以下之成分的量的下限較佳為35質量%、更佳為38質量%、進而較佳為40質量%、特佳為41質量%、最佳為42質量%。 在GPC累積曲線的分子量10萬以下之成分的量的上限,較佳為65質量%、更佳為60質量%、進而較佳為58質量%。在GPC累積曲線的分子量10萬以下之成分的量若為65質量%以下則膜強度不易降低。 此時,若包含緩和時間長的高分子量成分或長鏈分支成分,則變得易於調整聚丙烯樹脂所包含的分子量10萬以下之成分的量而不會大幅改變整體的黏度,故易於改善製膜性而不太會對剛性和熱收縮造成影響。That is, the lower limit of the amount of components with a molecular weight of 100,000 or less in the GPC (Gel Permeation Chromatography; gel permeation chromatography) accumulation curve of the polypropylene resin constituting the film of the present invention is preferably 35% by mass, more preferably 38% by mass, more preferably 40% by mass, particularly preferably 41% by mass, and most preferably 42% by mass. The upper limit of the amount of components with a molecular weight of 100,000 or less in the GPC accumulation curve is preferably 65 mass%, more preferably 60 mass%, and still more preferably 58 mass%. If the amount of components with a molecular weight of 100,000 or less in the GPC accumulation curve is 65% by mass or less, the film strength will not easily decrease. At this time, if a high molecular weight component or a long chain branch component with a long relaxation time is included, it becomes easy to adjust the amount of components with a molecular weight of 100,000 or less contained in the polypropylene resin without greatly changing the overall viscosity, so it is easy to improve the production process. Film properties without affecting rigidity and heat shrinkage.

[分子量分布] 本發明所使用的聚丙烯樹脂,作為分子量分布的廣度的指標之質量平均分子量(Mw)/數平均分子量(Mn)的下限較佳為3.5、更佳為4.0、進而較佳為4.5、特佳為5.0。Mw/Mn的上限較佳為30、更佳為25、進而較佳為23、特佳為21、最佳為20。 Mw/Mn能夠使用凝膠滲透層析法(GPC)來獲得。若Mw/Mn為上述範圍,就容易增加分子量10萬以下之成分的量。[The molecular weight distribution] For the polypropylene resin used in the present invention, the lower limit of the mass average molecular weight (Mw)/number average molecular weight (Mn), which is an indicator of the breadth of the molecular weight distribution, is preferably 3.5, more preferably 4.0, further preferably 4.5, and particularly preferably is 5.0. The upper limit of Mw/Mn is preferably 30, more preferably 25, further preferably 23, particularly preferably 21, and most preferably 20. Mw/Mn can be obtained using gel permeation chromatography (GPC). If Mw/Mn is in the above range, it is easy to increase the amount of components with a molecular weight of 100,000 or less.

另外,聚丙烯樹脂的分子量分布,能藉由將不同分子量的成分以多階段的一連串整套設備來聚合、或將不同分子量的成分在離線以混練機來摻合、或摻合具有不同性能之觸媒來聚合、或使用能夠實現期望的分子量分布之觸媒來調整。作為以GPC所獲得之分子量分布的形狀,在以分子量(M)的對數(logM)為橫軸,以微分分布値(每logM的重量分率)為縱軸的GPC圖表中,可以是具有單一波峰之平緩的分子量分布,也可以是具有複數的波峰和肩峰的分子量分布。In addition, the molecular weight distribution of polypropylene resin can be achieved by polymerizing components with different molecular weights in a multi-stage series of complete equipment, or by blending components with different molecular weights offline using a mixer, or by blending materials with different properties. Use a catalyst to polymerize, or use a catalyst that can achieve the desired molecular weight distribution. As the shape of the molecular weight distribution obtained by GPC, in a GPC chart with the logarithm (logM) of the molecular weight (M) as the horizontal axis and the differential distribution value (weight fraction per logM) as the vertical axis, a single A molecular weight distribution with a gentle peak may also be a molecular weight distribution with multiple peaks and shoulders.

[雙軸配向聚丙烯膜的製膜方法] 本發明之雙軸配向聚丙烯膜,較佳為藉由製作由將上述的聚丙烯樹脂作為主成分之聚丙烯樹脂組成物所構成的未延伸片,並進行雙軸延伸而獲得。作為雙軸延伸的方法,藉由吹脹同時雙軸延伸法、拉幅同時雙軸延伸法、拉幅逐次雙軸延伸法中的任一種都能獲得,但以製膜穩定性、厚度均一性的觀點較佳為採用拉幅逐次雙軸延伸法。尤其雖然較佳為在朝長度方向延伸後再朝寬度方向進行延伸,但也可以是在朝寬度方向延伸後再朝長度方向進行延伸之方法。[Film production method of biaxially oriented polypropylene film] The biaxially aligned polypropylene film of the present invention is preferably obtained by producing an unstretched sheet composed of a polypropylene resin composition containing the above-mentioned polypropylene resin as a main component and biaxially stretching the film. As a biaxial stretching method, any of the blowing simultaneous biaxial stretching method, the tenter simultaneous biaxial stretching method, and the tenter sequential biaxial stretching method can be obtained. However, film production stability and thickness uniformity are required. The better point of view is to use the stenter sequential biaxial stretching method. In particular, it is preferable to extend in the length direction and then extend in the width direction. However, it may also be a method of extending in the width direction and then extending in the length direction.

其次在以下說明本發明之雙軸配向聚丙烯膜的製造方法,但並不一定限定於此製造方法。另外,本發明之雙軸配向聚丙烯膜,亦可至少在單面積層具有其他機能之層。進行積層的可以是單面也可以是雙面。屆時只要另一方之層、或中央層的樹脂組成物是採用上述的聚丙烯樹脂組成物即可。又,也可以是與上述的聚丙烯樹脂組成物不同的聚丙烯樹脂組成物。積層之層的數量,雖然亦可每單面1層或2層、3層以上,但從製造的觀點而言,較佳為1層或2層。作為積層的方法,例如較佳為藉由進料塊方式或多歧管方式所為之共擠壓。尤其是以提升雙軸配向聚丙烯膜的加工性為目的,能夠將具有熱封性的樹脂層在不使特性降低的範圍進行積層。Next, the manufacturing method of the biaxially aligned polypropylene film of the present invention will be described below, but it is not necessarily limited to this manufacturing method. In addition, the biaxially aligned polypropylene film of the present invention may also be layered with layers having other functions on at least a single area. Lamination can be done on one side or two sides. In that case, it is sufficient that the resin composition of the other layer or the central layer is the above-mentioned polypropylene resin composition. Moreover, it may be a polypropylene resin composition different from the above-mentioned polypropylene resin composition. The number of laminated layers may be 1 layer, 2 layers, or 3 or more layers per side, but from a manufacturing viewpoint, 1 layer or 2 layers is preferred. As a lamination method, for example, co-extrusion by a feed block system or a multi-manifold system is preferred. In particular, for the purpose of improving the processability of the biaxially aligned polypropylene film, a resin layer having heat sealability can be laminated within a range that does not degrade the properties.

以下是針對單層的情況之例,並針對採用了拉幅逐次雙軸延伸法的情況來陳述。 首先,將包含聚丙烯樹脂的樹脂組成物以單軸或雙軸的擠壓機使之加熱熔融,從T字模擠壓成片狀,使之接觸冷卻輥來冷卻固化。以促進固化為目的,較佳為進行將經冷卻輥冷卻的片材浸漬於水槽等來進一步冷卻。The following is an example for a single layer and is stated for the case where the tenter sequential biaxial stretching method is used. First, a resin composition containing polypropylene resin is heated and melted using a uniaxial or biaxial extruder, and is extruded into a sheet form from a T-die, and is cooled and solidified by contacting a cooling roll. For the purpose of accelerating solidification, it is preferable to further cool the sheet cooled by a cooling roll by immersing it in a water tank or the like.

然後,以加熱了片材之2對的延伸輥,藉由增大後方的延伸輥的旋轉數而將片材朝長度方向延伸,獲得單軸延伸膜。Then, using two pairs of stretching rollers that heated the sheet, the sheet was stretched in the longitudinal direction by increasing the rotation number of the rear stretching roller, thereby obtaining a uniaxially stretched film.

接下來,將單軸延伸膜預熱後,以拉幅式延伸機一邊把持著膜端部,一邊以特定的溫度朝寬度方向進行延伸,獲得雙軸延伸膜。關於此寬度方向延伸步驟會在之後詳細敘述。Next, the uniaxially stretched film is preheated and then stretched in the width direction at a specific temperature while holding the ends of the film using a tenter-type stretching machine to obtain a biaxially stretched film. This step of extending in the width direction will be described in detail later.

寬度方向延伸步驟結束後,將雙軸延伸膜以特定的溫度進行熱處理,獲得雙軸配向膜。在熱處理步驟中,亦可將膜朝寬度方向進行弛緩。After the width direction stretching step is completed, the biaxially stretched film is heat treated at a specific temperature to obtain a biaxially aligned film. In the heat treatment step, the film may be relaxed in the width direction.

對於如此獲得的雙軸配向聚丙烯膜,能夠視需要例如藉由對至少單面施以電暈放電處理後,以捲繞機捲繞來獲得膜輥。The biaxially aligned polypropylene film thus obtained can be obtained by, for example, subjecting at least one side to corona discharge treatment and then winding it with a winding machine to obtain a film roll, if necessary.

以下針對各個的步驟詳細地說明。 [擠壓步驟] 首先,將以聚丙烯樹脂作為主成分之聚丙烯樹脂組成物用單軸或雙軸的擠壓機在200℃至300℃的範圍使之加熱熔融,擠壓出從T字模出來的片狀的熔融聚丙烯樹脂組成物,使之接觸金屬製的冷卻輥予以冷卻固化。獲得的未延伸片較佳為進一步投入水槽。 冷卻輥、或冷卻輥與水槽的溫度較佳為自10℃至Tc的範圍,在欲提高膜的透明性的情況,較佳為以10℃至50℃的範圍之溫度的冷卻輥來冷卻固化。若將冷卻溫度設為50℃以下則未延伸片的透明性易於提高,較佳為40℃以下、進而較佳為30℃以下。為了使逐次雙軸延伸後的結晶配向度增大,雖然有將冷卻溫度設為40℃以上亦佳的情況,但如上述般使用內消旋五單元組分率為97.0%以上的丙烯同元聚合物的情況,將冷卻溫度設為40℃以下則易於進行下一步驟的延伸,且在降低厚度不均方面較佳,設為30℃以下則更佳。 未延伸片的厚度設為3500μm以下,在冷卻效率方面較佳,進而較佳是設為3000μm以下,能夠依照逐次雙軸延伸後的膜厚度來適當調整。未延伸片的厚度能夠以聚丙烯樹脂組成物的擠壓速度及T字模的唇寬等來控制。Each step is explained in detail below. [Extrusion step] First, a polypropylene resin composition with polypropylene resin as the main component is heated and melted using a uniaxial or biaxial extruder in the range of 200°C to 300°C, and a sheet-like product is extruded from a T-shaped die. The polypropylene resin composition is melted and contacted with a metal cooling roller to cool and solidify. The obtained unstretched piece is preferably further put into a water tank. The temperature of the cooling roller or the cooling roller and the water tank is preferably in the range of 10°C to Tc. When the transparency of the film is to be improved, it is preferred to cool and solidify with a cooling roller having a temperature in the range of 10°C to 50°C. . If the cooling temperature is 50°C or lower, the transparency of the unstretched sheet will be easily improved, and it is preferably 40°C or lower, and further preferably 30°C or lower. In order to increase the degree of crystal orientation after sequential biaxial stretching, it is sometimes preferable to set the cooling temperature to 40°C or higher. However, as mentioned above, use a propylene homogenate with a meso pentad component ratio of 97.0% or higher. In the case of polymers, it is better to set the cooling temperature to 40°C or less to facilitate the next step of stretching and to reduce thickness unevenness, and to set the cooling temperature to 30°C or less is even more preferred. The thickness of the unstretched sheet is preferably 3,500 μm or less in terms of cooling efficiency, and is further preferably 3,000 μm or less, which can be appropriately adjusted according to the film thickness after sequential biaxial stretching. The thickness of the unstretched sheet can be controlled by the extrusion speed of the polypropylene resin composition, the lip width of the T-shaped die, and the like.

[長度方向延伸步驟] 長度方向延伸倍率的下限較佳為3倍、更佳為3.5倍、特佳為3.8倍。若為上述範圍則易於提高強度,膜厚不均也會減少。長度方向延伸倍率的上限較佳為8倍、更佳為7.5倍、特佳為7倍。若為上述範圍,易於進行在寬度方向延伸步驟之寬度方向延伸,生產性會提升。 長度方向延伸溫度的下限較佳為Tm-40℃、更佳為Tm-37℃、進而較佳為Tm-35℃。若為上述範圍則接續進行的寬度方向延伸會變得容易,膜厚不均也會減少。長度方向延伸溫度的上限較佳為Tm-7℃、更佳為Tm-10℃、進而較佳為Tm-12℃。若為上述範圍則易於縮小熱收縮率,不會因附著於延伸輥而變得不易延伸,或因表面的粗糙度變大而使品位降低的情形也較少。 另外,長度方向延伸可使用3對以上的延伸輥,而分成2階段以上的多階段來延伸。[Lengthwise extension steps] The lower limit of the longitudinal extension ratio is preferably 3 times, more preferably 3.5 times, and particularly preferably 3.8 times. If it is within the above range, the strength can be easily improved and film thickness unevenness can be reduced. The upper limit of the longitudinal extension ratio is preferably 8 times, more preferably 7.5 times, and particularly preferably 7 times. If it is within the above range, the width direction extension in the width direction extension step can be easily performed, and productivity will be improved. The lower limit of the longitudinal extension temperature is preferably Tm-40°C, more preferably Tm-37°C, and still more preferably Tm-35°C. If it is within the above range, subsequent stretching in the width direction will become easier, and film thickness unevenness will also be reduced. The upper limit of the longitudinal extension temperature is preferably Tm-7°C, more preferably Tm-10°C, and still more preferably Tm-12°C. If it is within the above range, the thermal shrinkage ratio can be easily reduced, and it is unlikely to become difficult to stretch due to adhesion to the stretching roller, or the quality will be reduced due to increased surface roughness. In addition, three or more pairs of stretching rollers may be used for longitudinal stretching, and the stretching may be divided into two or more stages.

[預熱步驟] 在寬度方向延伸步驟之前,有需要將長度方向延伸後的單軸延伸膜在Tm至Tm+25℃的範圍加熱,使聚丙烯樹脂組成物軟化。藉由設為Tm以上,軟化會進展,寬度方向的延伸變得容易。藉由設為Tm+25℃以下,橫延伸時的配向會進展,會變得易於展現剛性。更佳為Tm+2℃至Tm+22℃,特佳為Tm+3℃至Tm+20℃。此處,將在預熱步驟的最高溫度作為預熱溫度。[Preheating step] Before the step of stretching in the width direction, it is necessary to heat the uniaxially stretched film stretched in the length direction in the range of Tm to Tm+25°C to soften the polypropylene resin composition. By setting it to Tm or more, softening progresses and stretching in the width direction becomes easy. By setting the temperature to Tm+25°C or less, the alignment during lateral stretching progresses, making it easier to exhibit rigidity. More preferably, it is Tm+2°C to Tm+22°C, and particularly preferably, it is Tm+3°C to Tm+20°C. Here, the highest temperature in the preheating step is taken as the preheating temperature.

[寬度方向延伸步驟] 在預熱步驟後的寬度方向延伸步驟中,較佳的方法如以下所述。[Width direction extension procedure] In the width direction stretching step after the preheating step, a preferable method is as follows.

於寬度方向延伸步驟中,設置以Tm-10℃以上、預熱溫度以下的溫度進行延伸的區間(前期區間)。此時,前期區間的開始時可以是達到預熱溫度的時點,也可以是達到預熱溫度後使溫度下降而達到比預熱溫度還要低的溫度的時點。 寬度方向延伸步驟中之前期區間的溫度的下限較佳為Tm-9℃、更佳為Tm-8℃、進而較佳為Tm-7℃。若前期區間的延伸溫度在此範圍則不易發生延伸不均。 接續於前期區間,設置以低於前期區間的溫度、且為Tm-70℃以上至Tm-5℃以下的溫度進行延伸的區間(後期區間)。 後期區間的延伸溫度的上限較佳為Tm-8℃、更佳為Tm-10℃。後期區間的延伸溫度若在此範圍則會變得易於展現剛性。 後期區間的延伸溫度的下限較佳為Tm-65℃、更佳為Tm-60℃、進而較佳為Tm-55℃。後期區間的延伸溫度若在此範圍則製膜易於穩定。 後期區間結束時,亦即在到達寬度方向最終延伸倍率時,能夠馬上將膜冷卻。此時的冷卻的溫度,較佳是設為在後期區間的溫度以下,且為Tm-80℃以上至Tm-15℃以下的溫度、更佳是設為Tm-80℃以上至Tm-20℃以下的溫度、進而較佳是設為Tm-80℃以上至Tm-30℃以下的溫度、特佳是設為Tm-70℃以上至Tm-40℃以下的溫度。 前期區間的溫度及後期區間的溫度亦能夠慢慢地使之降低,也能夠以階段性或者一階段使之降低,亦可各自固定。若使溫度慢慢降低,膜不易斷裂,且膜的厚度變動也易於縮小。又,由於熱收縮率也易於縮小,膜的白化亦少因此較佳。 從寬度方向延伸步驟中之前期區間結束時的溫度到後期區間開始時的溫度,亦能夠慢慢地使之降低,也能夠以階段性或者一階段使之降低。In the width direction stretching step, a section (preliminary section) for stretching at a temperature of Tm-10° C. or higher and below the preheating temperature is provided. At this time, the start of the early period may be a time when the preheating temperature is reached, or a time when the temperature is lowered after reaching the preheating temperature to reach a temperature lower than the preheating temperature. The lower limit of the temperature in the previous section in the width direction stretching step is preferably Tm-9°C, more preferably Tm-8°C, and still more preferably Tm-7°C. If the extension temperature of the previous interval is within this range, uneven extension will not easily occur. Following the early stage section, a section (late stage section) extending at a temperature lower than the early stage section and extending from Tm-70°C or more to Tm-5°C or less is provided. The upper limit of the extension temperature in the later period is preferably Tm-8°C, more preferably Tm-10°C. If the extension temperature in the later period is within this range, it becomes easier to exhibit rigidity. The lower limit of the extension temperature in the later period is preferably Tm-65°C, more preferably Tm-60°C, and still more preferably Tm-55°C. If the extension temperature in the later period is within this range, film production will be easier to stabilize. At the end of the later period, that is, when the final stretching ratio in the width direction is reached, the film can be cooled immediately. The cooling temperature at this time is preferably lower than the temperature in the later period and is a temperature between Tm-80°C and Tm-15°C, and more preferably a temperature between Tm-80°C and Tm-20°C. The temperature below is more preferably Tm-80°C or more and Tm-30°C or less, particularly preferably Tm-70°C or more and Tm-40°C or less. The temperature in the early period and the temperature in the later period can be gradually lowered, can be lowered in stages or in one step, or can be fixed respectively. If the temperature is gradually lowered, the film is less likely to break and the thickness variation of the film is also likely to be reduced. In addition, the thermal shrinkage rate is also easy to reduce, and the whitening of the film is also less, which is preferable. In the width direction extending step, the temperature at the end of the previous section can be gradually reduced to the temperature at the start of the later section, or the temperature can be reduced in steps or in one step.

寬度方向延伸步驟之前期區間結束時的延伸倍率的下限較佳為4倍、更佳為5倍、進而較佳為6倍、特佳為6.5倍。前期區間結束時的延伸倍率的上限較佳為15倍、更佳為14倍、進而較佳為13倍。The lower limit of the stretching ratio at the end of the early period before the width direction stretching step is preferably 4 times, more preferably 5 times, further preferably 6 times, and particularly preferably 6.5 times. The upper limit of the stretch ratio at the end of the early period is preferably 15 times, more preferably 14 times, and still more preferably 13 times.

寬度方向延伸步驟中的最終寬度方向延伸倍率的下限較佳為5倍、更佳為6倍、進而較佳為7倍、特佳為8倍。若為5倍以上則易於提高剛性,亦變得易於減少膜厚不均。 寬度方向延伸倍率的上限較佳為20倍、更佳為17倍、進而較佳為15倍。若為20倍以下則易於縮小熱收縮率,在延伸時不易斷裂。The lower limit of the final width direction stretching ratio in the width direction stretching step is preferably 5 times, more preferably 6 times, further preferably 7 times, and particularly preferably 8 times. If it is 5 times or more, the rigidity will be easily improved and film thickness unevenness will be easily reduced. The upper limit of the width direction extension ratio is preferably 20 times, more preferably 17 times, and still more preferably 15 times. If it is 20 times or less, the thermal shrinkage rate will be reduced easily and it will be less likely to break during elongation.

如此一來,藉由使用立體規則性高且高熔點之結晶性高的聚丙烯樹脂,採用上述的寬度方向延伸步驟,即使不將延伸倍率極端地放大,由於聚丙烯樹脂的分子會高度地排列在主配向方向(在上述的寬度方向延伸步驟是對應為寬度方向),因此獲得的雙軸配向膜中的結晶配向非常強,易於生成熔點亦高的結晶。 又,由於結晶間之非晶部的配向亦在主配向方向(在上述的寬度方向延伸步驟是對應為寬度方向)提高,在非晶部的周圍存在許多熔點高的結晶,因此在低於結晶的熔點之溫度,非晶部之已伸長的聚丙烯分子不易緩和,而易於保持該聚丙烯分子張緊的狀態。因此,即使在高溫中雙軸配向膜整體能夠維持高的剛性。 再者,值得注意的是,藉由採用這樣的寬度方向延伸步驟,在150℃之高溫的熱收縮率也易於降低。這個理由是在於因為在非晶部的周圍存在許多熔點高的結晶,所以在低於結晶的熔點之溫度,非晶部中之已伸長的聚丙烯樹脂分子不易緩和,而且分子彼此的纏繞較少之故。In this way, by using a polypropylene resin with high stereoregularity and high melting point and high crystallinity, and using the above-mentioned width direction stretching step, the molecules of the polypropylene resin will be highly aligned even if the stretching magnification is not extremely amplified. In the main alignment direction (the above-mentioned stretching step in the width direction corresponds to the width direction), the crystal alignment in the biaxially aligned film obtained is very strong, and crystals with a high melting point are easily generated. In addition, since the alignment of the amorphous portion between crystals is also improved in the main alignment direction (the above-mentioned width direction stretching step corresponds to the width direction), there are many crystals with high melting points around the amorphous portion, so it is lower than the crystalline At a temperature above the melting point, the elongated polypropylene molecules in the amorphous part are not easily relaxed, and it is easy to maintain the tense state of the polypropylene molecules. Therefore, the entire biaxial alignment film can maintain high rigidity even at high temperatures. Furthermore, it is worth noting that by adopting such a width direction stretching step, the thermal shrinkage rate at a high temperature of 150°C is also easily reduced. The reason for this is that there are many crystals with high melting points around the amorphous part. Therefore, at a temperature lower than the melting point of the crystal, the elongated polypropylene resin molecules in the amorphous part are not easy to relax, and the molecules are less entangled with each other. The reason.

進而值得注意的是,因為增加了聚丙烯樹脂的低分子量成分,所以膜的結晶度變得易於更加提高,並且非晶部分的聚丙烯樹脂分子鏈彼此的纏繞會變得更少,減弱熱收縮應力,藉此能夠使熱收縮率更加降低。若考量到習知有著若是提升了強度與熱收縮率的其中一方,則另一方的特性就會降低之傾向,則可以說本發明是劃時代的。Furthermore, it is worth noting that by increasing the low molecular weight component of polypropylene resin, the crystallinity of the film becomes easier to increase, and the polypropylene resin molecular chains in the amorphous part become less entangled with each other, weakening thermal shrinkage. Stress, whereby the thermal shrinkage rate can be further reduced. Taking into account the conventional wisdom that if one of the strength and thermal shrinkage is increased, the properties of the other will decrease, it can be said that the present invention is epoch-making.

[熱處理步驟] 雙軸延伸膜視需要能夠為了進一步縮小熱收縮率而進行熱處理。 熱處理溫度的上限較佳為Tm+10℃、更佳為Tm+7℃。藉由設為Tm+10℃以下,剛性易於展現,膜表面的粗糙度不會變得太大,膜不易白化。 熱處理溫度的下限較佳為Tm-10℃、更佳為Tm-7℃。若未達Tm-10℃則會有熱收縮率變高的情形。 藉由採用上述的寬度方向延伸步驟,即使以從Tm-10℃至Tm+10之間的溫度進行熱處理,在延伸步驟所生成的配向高的結晶不易熔化,能夠不使獲得的膜的剛性降低而更加縮小熱收縮率。 以調整熱收縮率為目的,可在熱處理時朝寬度方向使膜弛緩(緩和)。弛緩率的上限較佳為10%。若在上述範圍內,膜強度不易降低,膜厚度變動易於變小。更佳為8%、進而較佳為7%、又更佳為3%、特佳為2%、最佳為0%。[Heat treatment step] If necessary, the biaxially stretched film can be heat-treated in order to further reduce the thermal shrinkage rate. The upper limit of the heat treatment temperature is preferably Tm+10°C, more preferably Tm+7°C. By setting it to Tm+10°C or less, rigidity is easily exhibited, the roughness of the film surface does not become too large, and the film is less likely to whiten. The lower limit of the heat treatment temperature is preferably Tm-10°C, more preferably Tm-7°C. If the temperature is less than Tm-10°C, the thermal shrinkage rate may become high. By adopting the above-mentioned width direction stretching step, even if the heat treatment is performed at a temperature between Tm-10°C and Tm+10, the highly aligned crystals generated in the stretching step are less likely to melt, and the rigidity of the obtained film can not be reduced. And further reduce the thermal shrinkage rate. In order to adjust the heat shrinkage rate, the film can be relaxed (relaxed) in the width direction during heat treatment. The upper limit of the relaxation rate is preferably 10%. If it is within the above range, the film strength is less likely to decrease and the film thickness variation is likely to be smaller. More preferably, it is 8%, still more preferably, 7%, still more preferably, 3%, particularly preferably, 2%, and most preferably, 0%.

[膜厚度] 本發明之雙軸配向聚丙烯膜的厚度可配合各用途來設定,就獲得膜的強度而言,膜厚度的下限較佳為2μm、更佳為3μm、進而較佳為4μm、特佳為8μm、最佳為10μm。若膜厚度為2μm以上則易於獲得膜的剛性。膜厚度的上限較佳為100μm、更佳為80μm、進而較佳為60μm、特佳為50μm、最佳為40μm。若膜厚度為100μm以下則擠壓步驟時的未延伸片之冷卻速度不易變慢。 本發明之雙軸配向聚丙烯膜係通常是以寬度2000mm至12000mm、長度1000m至50000m左右的輥來製膜,捲繞成膜輥狀。並且,配合各用途而分切,以寬度300mm至2000mm、長度500m至5000m左右的分切輥來供應。本發明之雙軸配向聚丙烯膜能獲得更長的膜輥。[film thickness] The thickness of the biaxially aligned polypropylene film of the present invention can be set according to various uses. In terms of obtaining the strength of the film, the lower limit of the film thickness is preferably 2 μm, more preferably 3 μm, further preferably 4 μm, and particularly preferably 8 μm. , the best is 10μm. When the film thickness is 2 μm or more, the rigidity of the film can be easily obtained. The upper limit of the film thickness is preferably 100 μm, more preferably 80 μm, further preferably 60 μm, particularly preferably 50 μm, and most preferably 40 μm. If the film thickness is 100 μm or less, the cooling rate of the unstretched sheet during the extrusion step is less likely to slow down. The biaxially aligned polypropylene film system of the present invention is usually formed using a roll with a width of 2000mm to 12000mm and a length of about 1000m to 50000m, and is wound into a film roll shape. In addition, slitting rollers are supplied to suit each application, with a width of 300mm to 2000mm and a length of about 500m to 5000m. The biaxially aligned polypropylene film of the present invention can obtain longer film rolls.

[厚度均一性] 本發明之雙軸配向聚丙烯膜的厚度均一性的下限較佳為0%、更佳為0.1%、進而較佳為0.5%、特佳為1%。厚度均一性的上限較佳為20%、更佳為17%、進而較佳為15%、特佳為12%、最佳為10%。若為上述範圍則在塗佈或印刷等之後加工時不易產生不良,而易於用在被要求精密性的用途。 測定方法如同下述所為。在膜的長度方向從膜物性維持穩定的恆定區切出寬度方向40mm的試驗片,使用MIKURON計測器股份有限公司製造的膜進料裝置(使用製造編號:A90172)及安立知(ANRITSU)股份有限公司製造的膜厚度連續測定器(產品名:K-313A廣範圍高感度電子測微器),經過20000mm連續測量膜厚度,從下式算出厚度均一性。 厚度均一性(%)=[(厚度的最大値-厚度的最低値)/厚度的平均値]×100[Thickness Uniformity] The lower limit of the thickness uniformity of the biaxially aligned polypropylene film of the present invention is preferably 0%, more preferably 0.1%, further preferably 0.5%, and particularly preferably 1%. The upper limit of thickness uniformity is preferably 20%, more preferably 17%, further preferably 15%, particularly preferably 12%, and most preferably 10%. If it is within the above range, defects are less likely to occur during subsequent processing such as coating or printing, and it is easy to use it in applications requiring precision. The measurement method is as follows. A test piece with a width of 40 mm was cut out in the length direction of the film from a constant zone where the film physical properties are stable, and a film feeding device manufactured by MIKURON Measuring Instruments Co., Ltd. (manufacturing number: A90172) and ANRITSU Co., Ltd. The film thickness continuous measuring device manufactured by the company (product name: K-313A wide-range high-sensitivity electronic micrometer) continuously measures the film thickness through 20000mm, and calculates the thickness uniformity from the following formula. Thickness uniformity (%) = [(maximum value of thickness - minimum value of thickness)/average value of thickness] × 100

[膜特性] 本發明之雙軸配向聚丙烯膜的特徵在於下述特性。此處,在本發明之雙軸配向聚丙烯膜中所謂的「長度方向」,係對應於膜製造步驟中的流向之方向,所謂的「寬度方向」,係正交於前述的膜製造步驟中的流向之方向。針對膜製造步驟中的流向不明的聚丙烯膜,對於膜表面朝垂直方向入射廣角X射線,在圓周方向掃描源自α型結晶的(110)面之散射峰,將獲得的繞射強度分布之繞射強度最大的方向作為「長度方向」,並將正交於該長度方向之方向作為「寬度方向」。[Film characteristics] The biaxially aligned polypropylene film of the present invention is characterized by the following properties. Here, in the biaxially aligned polypropylene film of the present invention, the so-called "longitudinal direction" corresponds to the direction of flow in the film production step, and the so-called "width direction" is orthogonal to the aforementioned film production step. The direction of flow. For a polypropylene film whose flow direction is unknown in the film manufacturing process, wide-angle X-rays are incident on the film surface in the vertical direction, and the scattering peak originating from the (110) plane of the α-type crystal is scanned in the circumferential direction. The obtained diffraction intensity distribution is The direction with the greatest diffraction intensity is regarded as the "longitudinal direction", and the direction orthogonal to the longitudinal direction is regarded as the "width direction".

[TMA加熱伸長] 本發明之雙軸配向聚丙烯膜之以熱機械分析裝置所測定在長度方向於150℃以下的最大伸長量的上限為1.5mm、較佳為1.45mm、更佳為1.4mm、進而較佳為1.35mm、特佳為1.3mm。若在上述範圍,則有在輥的加熱加工和印刷時的變形較小,加工性會提升的情況。在長度方向於150℃以下的最大伸長量的下限較佳為0.5mm、更佳為0.6mm、進而較佳為0.7mm、特佳為0.75mm、最佳為0.8mm。若在上述範圍,則有變得容易實際地製造的情況。 在寬度方向於150℃以下的最大伸長量的上限為0.1mm、較佳為0.09mm、更佳為0.08mm、進而較佳為0.075mm、特佳為0.07mm。在寬度方向於150℃以下的最大伸長量的下限較佳為0.005mm、更佳為0.01mm、進而較佳為0.015mm、特佳為0.018mm、最佳為0.2mm。若在上述範圍,則有變形較小且外觀提升的情況。[TMA heating elongation] The upper limit of the maximum elongation of the biaxially aligned polypropylene film of the present invention in the length direction below 150°C as measured by a thermomechanical analysis device is 1.5 mm, preferably 1.45 mm, more preferably 1.4 mm, and further preferably 1.35mm, the best is 1.3mm. If it is within the above range, deformation during heating processing of the roller and printing may be small, and workability may be improved. The lower limit of the maximum elongation in the longitudinal direction below 150° C. is preferably 0.5 mm, more preferably 0.6 mm, further preferably 0.7 mm, particularly preferably 0.75 mm, most preferably 0.8 mm. If it is within the above range, actual production may become easier. The upper limit of the maximum elongation in the width direction below 150° C. is 0.1 mm, preferably 0.09 mm, more preferably 0.08 mm, further preferably 0.075 mm, particularly preferably 0.07 mm. The lower limit of the maximum elongation in the width direction below 150° C. is preferably 0.005 mm, more preferably 0.01 mm, further preferably 0.015 mm, particularly preferably 0.018 mm, most preferably 0.2 mm. If it is within the above range, the deformation may be smaller and the appearance may be improved.

[150℃熱收縮率] 本發明之雙軸配向聚丙烯膜在150℃的長度方向之熱收縮率的上限為10%、較佳為8.0%、更佳為7.0%。在150℃的寬度方向之熱收縮率的上限為30%、較佳為25%、更佳為20%。若長度方向的熱收縮率為10%以下,且寬度方向的熱收縮率為30%以下,熱封時不易產生皺褶,尤其若在150℃的長度方向之熱收縮率為8.0%以下,在150℃的寬度方向之熱收縮率為20%以下,則在開口部熔接夾鏈部時的應變較小而較佳。就縮小在150℃的熱收縮率而言,將測定了構成膜之聚丙烯樹脂的凝膠滲透層析法(GPC)累積曲線時的分子量10萬以下之成分的量的下限設為35質量%是有效的。[Thermal shrinkage rate at 150℃] The upper limit of the thermal shrinkage rate of the biaxially aligned polypropylene film of the present invention in the length direction at 150°C is 10%, preferably 8.0%, and more preferably 7.0%. The upper limit of the thermal shrinkage rate in the width direction at 150° C. is 30%, preferably 25%, and more preferably 20%. If the heat shrinkage rate in the length direction is less than 10% and the heat shrinkage rate in the width direction is less than 30%, wrinkles will not easily occur during heat sealing. Especially if the heat shrinkage rate in the length direction at 150°C is less than 8.0%, it will It is preferable that the thermal shrinkage rate in the width direction at 150°C is 20% or less, so that the strain when welding the clip portion at the opening is small. In terms of thermal shrinkage at 150°C, the lower limit of the amount of components with a molecular weight of 100,000 or less when the gel permeation chromatography (GPC) accumulation curve of the polypropylene resin constituting the film is measured is 35% by mass. It is effective.

本發明之雙軸配向聚丙烯膜若有下述特性、結構則更好。 [23℃楊氏模數] 本發明之雙軸配向聚丙烯膜在23℃的長度方向之楊氏模數的下限較佳為2.0GPa、更佳為2.1GPa、進而較佳為2.2GPa、特佳為2.3GPa、最佳為2.4GPa。在2.0GPa以上,由於剛性高,易於保持作為包裝袋時的袋狀,在印刷等加工時不易引起膜的變形。長度方向之楊氏模數的上限較佳為4.0GPa、更佳為3.8GPa、進而較佳為3.7GPa、特佳為3.6GPa、最佳為3.5GPa。在4.0GPa以下則容易實際地製造,又易於改善長度方向-寬度方向之特性的平衡。It would be better if the biaxially aligned polypropylene film of the present invention has the following characteristics and structure. [Young’s modulus at 23°C] The lower limit of the Young's modulus of the biaxially aligned polypropylene film of the present invention in the length direction at 23° C. is preferably 2.0 GPa, more preferably 2.1 GPa, further preferably 2.2 GPa, particularly preferably 2.3 GPa, and most preferably 2.4GPa. Above 2.0 GPa, due to its high rigidity, it is easy to maintain the bag shape when used as a packaging bag, and it is less likely to cause deformation of the film during processing such as printing. The upper limit of the Young's modulus in the length direction is preferably 4.0 GPa, more preferably 3.8 GPa, further preferably 3.7 GPa, particularly preferably 3.6 GPa, and most preferably 3.5 GPa. When it is below 4.0 GPa, it is easy to actually produce it, and it is easy to improve the balance of the characteristics in the length direction and the width direction.

本發明之雙軸配向聚丙烯膜在23℃的寬度方向之楊氏模數的下限較佳為6.0GPa、更佳為6.3GPa、進而較佳為6.5GPa、特佳為6.7GPa。在6.0GPa以上,由於剛性高,易於保持作為包裝袋時的袋狀,在印刷等加工時不易引起膜的變形。寬度方向之楊氏模數的上限較佳為15GPa、更佳為13GPa、進而較佳為12GPa。若在15GPa以下則容易實際地製造,又易於改善長度方向-寬度方向之特性的平衡。 楊氏模數能夠藉由調節延伸倍率和鬆弛率,或是調整製膜時的溫度而設在範圍內。The lower limit of the Young's modulus of the biaxially aligned polypropylene film of the present invention in the width direction at 23° C. is preferably 6.0 GPa, more preferably 6.3 GPa, further preferably 6.5 GPa, and particularly preferably 6.7 GPa. Above 6.0 GPa, due to its high rigidity, it is easy to maintain the bag shape when used as a packaging bag, and it is less likely to cause deformation of the film during processing such as printing. The upper limit of the Young's modulus in the width direction is preferably 15 GPa, more preferably 13 GPa, and still more preferably 12 GPa. If it is 15 GPa or less, it will be easy to actually produce it, and it will be easy to improve the balance of the longitudinal direction-width direction characteristics. Young's modulus can be set within a range by adjusting the stretch ratio and relaxation rate, or adjusting the temperature during film production.

[80℃楊氏模數] 本發明之雙軸配向聚丙烯膜在80℃中的長度方向之楊氏模數的下限較佳為0.5GPa、更佳為0.7GPa。在0.5GPa以上,則變得不易產生將高溫的印刷墨液轉印時的印刷間距偏差。在80℃中的長度方向之楊氏模數的上限較佳為3.0GPa、更佳為2.5GPa。在3.0GPa以上則容易實際地製造。 在80℃中的寬度方向之楊氏模數的下限較佳為2.5GPa、更佳為2.8GPa、進而較佳為3.0GPa。在2.5GPa以上,則變得不易產生將高溫的印刷墨液轉印時的印刷間距偏差。在80℃中的寬度方向之楊氏模數的上限較佳為5.0GPa、更佳為4.7GPa、進而較佳為4.5GPa。若在5.0GPa以下則容易實際地製造。 在80℃中的楊氏模數能夠藉由調整延伸倍率、延伸溫度、熱固定溫度而設在範圍內。[80°C Young’s modulus] The lower limit of the Young's modulus in the length direction of the biaxially aligned polypropylene film of the present invention at 80° C. is preferably 0.5 GPa, more preferably 0.7 GPa. When it is 0.5 GPa or more, printing pitch deviation becomes less likely to occur when high-temperature printing ink is transferred. The upper limit of the Young's modulus in the longitudinal direction at 80° C. is preferably 3.0 GPa, more preferably 2.5 GPa. Above 3.0 GPa, it is easy to actually manufacture. The lower limit of the Young's modulus in the width direction at 80° C. is preferably 2.5 GPa, more preferably 2.8 GPa, and still more preferably 3.0 GPa. When it is 2.5 GPa or more, printing pitch deviation becomes less likely to occur when high-temperature printing ink is transferred. The upper limit of the Young's modulus in the width direction at 80° C. is preferably 5.0 GPa, more preferably 4.7 GPa, and still more preferably 4.5 GPa. If it is 5.0 GPa or less, it will be easy to actually manufacture. The Young's modulus at 80° C. can be set within the range by adjusting the stretching ratio, stretching temperature, and heat fixing temperature.

[23℃5%伸長時的應力] 本發明之雙軸配向聚丙烯膜在23℃的長度方向之5%伸長時的應力(F5)的下限為40MPa、較佳為42MPa、更佳為43MPa、進而較佳為44MPa、特佳為45MPa。在40MPa以上,由於剛性高,易於保持作為包裝袋時的袋狀,在印刷等加工時不易引起膜的變形。長度方向之F5的上限較佳為70MPa、更佳為65MPa、進而較佳為62MPa、特佳為61MPa、最佳為60MPa。在70MPa以下則容易實際地製造,又易於改善長-寬平衡。 本發明之雙軸配向聚丙烯膜在23℃的寬度方向之F5的下限為160MPa、較佳為165MPa、更佳為168MPa、進而較佳為170MPa。在160MPa以上,由於剛性高,易於保持作為包裝袋時的袋狀,在印刷等加工時不易引起膜的變形。寬度方向之F5的上限較佳為250MPa、更佳為245MPa、進而較佳為240MPa。若在250MPa以下則容易實際地製造,又易於改善長-寬平衡。 F5能夠藉由調節延伸倍率和鬆弛率,或是調整製膜時的溫度而設在範圍內。 [80℃5%伸長時的應力] 本發明之雙軸配向聚丙烯膜在80℃的長度方向之5%伸長時的應力(F5)的下限為15MPa、較佳為17MPa、更佳為19MPa、進而較佳為20MPa。在15MPa以上,由於剛性高,易於保持作為包裝袋時的袋狀,在印刷等加工時不易引起膜的變形。長度方向之在80℃的F5的上限較佳為40MPa、更佳為35MPa、進而較佳為30MPa、特佳為25MPa。在40MPa以下則容易實際地製造,又易於改善長-寬平衡。 本發明之雙軸配向聚丙烯膜在80℃的寬度方向之F5的下限為75MPa、較佳為80MPa、更佳為85MPa、進而較佳為90MPa、特佳為95MPa。在75MPa以上,由於剛性高,易於保持作為包裝袋時的袋狀,在印刷等加工時不易引起膜的變形。寬度方向之在80℃的F5的上限較佳為150MPa、更佳為140MPa、進而較佳為130MPa。若在140MPa以下則容易實際地製造,又易於改善長-寬平衡。 80℃的F5能夠藉由調節延伸倍率和鬆弛率,或是調整製膜時的溫度而設在範圍內。[Stress at 5% elongation at 23°C] The lower limit of the stress (F5) of the biaxially aligned polypropylene film of the present invention at 5% elongation in the length direction at 23°C is 40MPa, preferably 42MPa, more preferably 43MPa, further preferably 44MPa, and particularly preferably 45MPa. . Above 40 MPa, due to high rigidity, it is easy to maintain the bag shape when used as a packaging bag, and is less likely to cause deformation of the film during processing such as printing. The upper limit of F5 in the length direction is preferably 70MPa, more preferably 65MPa, further preferably 62MPa, particularly preferably 61MPa, and most preferably 60MPa. Below 70 MPa, it is easy to actually manufacture and it is easy to improve the length-width balance. The lower limit of F5 in the width direction of the biaxially aligned polypropylene film of the present invention at 23° C. is 160 MPa, preferably 165 MPa, more preferably 168 MPa, and still more preferably 170 MPa. Above 160MPa, due to its high rigidity, it is easy to maintain the bag shape when used as a packaging bag, and is less likely to cause deformation of the film during processing such as printing. The upper limit of F5 in the width direction is preferably 250MPa, more preferably 245MPa, and still more preferably 240MPa. If it is 250 MPa or less, it will be easy to actually manufacture and it will be easy to improve the length-width balance. F5 can be set within the range by adjusting the stretch ratio and relaxation ratio, or adjusting the temperature during film production. [Stress at 5% elongation at 80°C] The lower limit of the stress (F5) of the biaxially aligned polypropylene film of the present invention at 5% elongation in the length direction at 80° C. is 15 MPa, preferably 17 MPa, more preferably 19 MPa, and still more preferably 20 MPa. At 15 MPa or above, due to its high rigidity, it is easy to maintain the bag shape when used as a packaging bag, and it is less likely to cause deformation of the film during processing such as printing. The upper limit of F5 at 80°C in the longitudinal direction is preferably 40 MPa, more preferably 35 MPa, further preferably 30 MPa, and particularly preferably 25 MPa. Below 40 MPa, it is easy to actually manufacture and it is easy to improve the length-width balance. The lower limit of F5 in the width direction of the biaxially aligned polypropylene film of the present invention at 80°C is 75MPa, preferably 80MPa, more preferably 85MPa, further preferably 90MPa, and particularly preferably 95MPa. Above 75MPa, due to its high rigidity, it is easy to maintain the bag shape when used as a packaging bag, and it is less likely to cause film deformation during printing and other processing. The upper limit of F5 at 80° C. in the width direction is preferably 150 MPa, more preferably 140 MPa, and still more preferably 130 MPa. If it is 140 MPa or less, it will be easy to actually manufacture and it will be easy to improve the length-width balance. F5 at 80°C can be set within the range by adjusting the stretch ratio and relaxation rate, or adjusting the temperature during film production.

[120℃熱收縮率] 本發明之雙軸配向聚丙烯膜在120℃的長度方向之熱收縮率的上限較佳為2.0%、更佳為1.7%、進而較佳為1.5%。若為2.0%以下,則變得不易產生將印刷墨液轉印時的印刷間距偏差。在120℃的寬度方向之熱收縮率的上限為5.0%、較佳為4.5%、更佳為4.0%。若為5.0%以下,則熱封時不易產生皺褶。 若在120℃的長度方向熱收縮率小於在120℃的寬度方向熱收縮率,則變得更不易產生將印刷墨液轉印時的印刷間距偏差。在120℃的熱收縮率、與熱收縮率的長度方向-寬度方向之平衡能夠藉由調整延伸倍率、延伸溫度、熱固定溫度而設在範圍內。[Thermal shrinkage rate at 120℃] The upper limit of the thermal shrinkage rate of the biaxially aligned polypropylene film of the present invention in the length direction at 120° C. is preferably 2.0%, more preferably 1.7%, and still more preferably 1.5%. If it is 2.0% or less, printing pitch deviation will be less likely to occur when printing ink is transferred. The upper limit of the thermal shrinkage rate in the width direction at 120°C is 5.0%, preferably 4.5%, more preferably 4.0%. If it is 5.0% or less, wrinkles will not easily occur during heat sealing. If the thermal shrinkage rate in the longitudinal direction at 120° C. is smaller than the thermal shrinkage rate in the width direction at 120° C., printing pitch deviation when transferring printing ink becomes less likely to occur. The heat shrinkage rate at 120°C and the balance between the length direction and the width direction of the heat shrinkage rate can be set within the range by adjusting the stretching ratio, stretching temperature, and heat fixing temperature.

[折射率] 本發明之雙軸配向聚丙烯膜的長度方向的折射率(Nx)的下限較佳為1.4950、更佳為1.4970、進而較佳為1.4980。若為1.4950以上則易於提高膜的剛性。長度方向的折射率(Nx)的上限較佳為1.5100、更佳為1.5070、進而較佳為1.5050。若為1.5100以下則易使膜的長度方向-寬度方向之特性的平衡優異。[Refractive index] The lower limit of the refractive index (Nx) in the longitudinal direction of the biaxially aligned polypropylene film of the present invention is preferably 1.4950, more preferably 1.4970, and still more preferably 1.4980. If it is 1.4950 or more, it is easy to increase the rigidity of a film. The upper limit of the refractive index (Nx) in the longitudinal direction is preferably 1.5100, more preferably 1.5070, and still more preferably 1.5050. If it is 1.5100 or less, it is easy to achieve an excellent balance between the longitudinal direction-width direction characteristics of the film.

本發明之雙軸配向聚丙烯膜的寬度方向的折射率(Ny)的下限為1.5230、較佳為1.5235、更佳為1.5240。若為1.5230以上則易於提高膜的剛性。寬度方向的折射率(Ny)的上限較佳為1.5280、更佳為1.5275、進而較佳為1.5270。若為1.5280以下則易使膜的長度方向-寬度方向之特性的平衡優異。The lower limit of the refractive index (Ny) in the width direction of the biaxially aligned polypropylene film of the present invention is 1.5230, preferably 1.5235, and more preferably 1.5240. If it is 1.5230 or more, the rigidity of the film will be easily improved. The upper limit of the refractive index (Ny) in the width direction is preferably 1.5280, more preferably 1.5275, and still more preferably 1.5270. If it is 1.5280 or less, it is easy to achieve an excellent balance between the longitudinal direction-width direction characteristics of the film.

本發明之雙軸配向聚丙烯膜的厚度方向的折射率(Nz)的下限較佳為1.4960、更佳為1.4965、進而較佳為1.4970。若為1.4960以上則易於提高膜的剛性。厚度方向的折射率(Nz)的上限較佳為1.5020、更佳為1.5015、進而較佳為1.5010。若為1.5020以下則易於提高膜的耐熱性。 折射率能夠藉由調整延伸倍率、延伸溫度、熱固定溫度而設在範圍內。The lower limit of the refractive index (Nz) in the thickness direction of the biaxially aligned polypropylene film of the present invention is preferably 1.4960, more preferably 1.4965, and still more preferably 1.4970. If it is 1.4960 or more, the rigidity of the membrane will be easily improved. The upper limit of the refractive index (Nz) in the thickness direction is preferably 1.5020, more preferably 1.5015, and still more preferably 1.5010. If it is 1.5020 or less, the heat resistance of the film will be easily improved. The refractive index can be set within a range by adjusting the extension magnification, extension temperature, and heat fixing temperature.

[ΔNy] 本發明之雙軸配向聚丙烯膜的ΔNy的下限為0.0220、較佳為0.0225、更佳為0.0228、進而較佳為0.0230。若為0.0220以上則膜的剛性容易提高。ΔNy的上限就實際的數值而言較佳為0.0270、更佳為0.0265、進而較佳為0.0262、特佳為0.0260。若為0.0270以下則厚度不均也易於變得良好。ΔNy能夠藉由調整膜的延伸倍率、延伸溫度、熱固定溫度而設在範圍內。 ΔNy的意思是將沿著膜的長度方向、寬度方向、厚度方向的折射率分別設為Nx、Ny、Nz並以下述式計算,而在膜的長度方向、寬度方向、厚度方向整體的配向之中的寬度方向的配向的程度。 ΔNy=Ny-[(Nx+Nz)/2][ΔNy] The lower limit of ΔNy of the biaxially aligned polypropylene film of the present invention is 0.0220, preferably 0.0225, more preferably 0.0228, and still more preferably 0.0230. If it is 0.0220 or more, the rigidity of the film will be easily improved. As for the actual numerical value, the upper limit of ΔNy is preferably 0.0270, more preferably 0.0265, still more preferably 0.0262, and particularly preferably 0.0260. If it is 0.0270 or less, thickness unevenness will tend to become good. ΔNy can be set within the range by adjusting the stretching ratio, stretching temperature, and heat fixing temperature of the film. ΔNy means that the refractive index along the length direction, width direction, and thickness direction of the film is set to Nx, Ny, and Nz respectively and calculated by the following formula, and the overall alignment of the film in the length direction, width direction, and thickness direction The degree of alignment in the width direction. ΔNy=Ny-[(Nx+Nz)/2]

[面配向係數] 本發明之雙軸配向聚丙烯膜的面配向係數(ΔP)的下限較佳為0.0135、更佳為0.0138、進而較佳為0.0140。若為0.0135以上則膜的面方向的平衡為良好,且厚度不均亦良好。面配向係數(ΔP)的上限就實際的數值而言較佳為0.0155、更佳為0.0152、進而較佳為0.0150。若為0.0155以下則易使在高溫的耐熱性優異。 面配向係數(ΔP)能夠藉由調整延伸倍率、延伸溫度、熱固定溫度而設在範圍內。 又,面配向係數(ΔP)是用(式)[(Nx+Ny)/2]-Nz來計算。[Plane alignment coefficient] The lower limit of the plane alignment coefficient (ΔP) of the biaxially aligned polypropylene film of the present invention is preferably 0.0135, more preferably 0.0138, and still more preferably 0.0140. If it is 0.0135 or more, the balance in the plane direction of the film will be good, and thickness unevenness will also be good. As for the actual numerical value, the upper limit of the plane alignment coefficient (ΔP) is preferably 0.0155, more preferably 0.0152, and still more preferably 0.0150. If it is 0.0155 or less, it is easy to achieve excellent heat resistance at high temperatures. The plane alignment coefficient (ΔP) can be set within a range by adjusting the stretching ratio, stretching temperature, and heat fixing temperature. In addition, the plane alignment coefficient (ΔP) is calculated using (formula) [(Nx+Ny)/2]-Nz.

[霧度] 本發明之雙軸配向聚丙烯膜的霧度的上限較佳為5.0%、更佳為4.5%、進而較佳為4.0%、特佳為3.5%、最佳為3.0%。若為5.0%以下則易於使用在要求透明的用途。霧度的下限就實際的數值而言較佳為0.1%、更佳為0.2%、進而較佳為0.3%、特佳為0.4%。若為0.1%以上則易於製造。霧度雖然能夠藉由調節冷卻輥(CR)溫度、寬度方向延伸溫度、拉幅機寬度方向延伸前預熱溫度、寬度方向延伸溫度、或熱固定溫度、或是聚丙烯樹脂的分子量為10萬以下之成分的量而設在範圍內,但是會有因為抗黏連劑的添加和賦予密封層而變大的情形。[Haze] The upper limit of the haze of the biaxially aligned polypropylene film of the present invention is preferably 5.0%, more preferably 4.5%, further preferably 4.0%, particularly preferably 3.5%, and most preferably 3.0%. If it is 5.0% or less, it is easy to use in applications requiring transparency. As for the actual numerical value, the lower limit of the haze is preferably 0.1%, more preferably 0.2%, further preferably 0.3%, and particularly preferably 0.4%. If it is 0.1% or more, it will be easy to manufacture. Although the haze can be adjusted by adjusting the cooling roll (CR) temperature, width direction extension temperature, preheating temperature before width direction extension of the tenter, width direction extension temperature, or heat fixing temperature, or the molecular weight of the polypropylene resin is 100,000 The amounts of the following components are set within the range, but may become larger due to the addition of an anti-blocking agent and the provision of a sealing layer.

[源自配向結晶之繞射峰的半值寬度] 本發明之雙軸配向聚丙烯膜在垂直於膜面入射之廣角X射線測定所獲得的聚丙烯α型結晶的(110)面之散射峰的方位角相依性中,源自膜的寬度方向的配向結晶之繞射峰的半值寬度(Wh)的上限較佳為27°、更佳為26°、進而較佳為25°、特佳為24°、最佳為23°。Wh的下限較佳為13°、更佳為14°、進而較佳為15°。若半值寬度(Wh)為27°以下則易於提高膜的剛性。[Half-value width of diffraction peak derived from aligned crystals] In the biaxially aligned polypropylene film of the present invention, the azimuthal dependence of the scattering peak of the (110) plane of the polypropylene α-type crystal obtained by wide-angle X-ray measurement perpendicular to the film surface is derived from the width direction of the film. The upper limit of the half-maximum width (Wh) of the diffraction peak of the aligned crystal is preferably 27°, more preferably 26°, further preferably 25°, particularly preferably 24°, and most preferably 23°. The lower limit of Wh is preferably 13°, more preferably 14°, and still more preferably 15°. When the half-value width (Wh) is 27° or less, the rigidity of the film can be easily improved.

[X射線配向度] 從本發明之雙軸配向聚丙烯膜的Wh並以下述式所算出之X射線配向度的下限較佳為0.85、更佳為0.855、進而較佳為0.861。藉由設為0.85以上而易於提高剛性。 X射線配向度=(180-Wh)/180 X射線配向度的上限較佳為0.928、更佳為0.922、進而較佳為0.917。藉由設為0.928以下而易使製膜穩定。[X-ray alignment degree] The lower limit of the X-ray alignment degree calculated from the Wh of the biaxially aligned polypropylene film of the present invention according to the following formula is preferably 0.85, more preferably 0.855, and still more preferably 0.861. By setting it to 0.85 or more, the rigidity can be easily improved. X-ray alignment degree=(180-Wh)/180 The upper limit of the X-ray alignment degree is preferably 0.928, more preferably 0.922, and still more preferably 0.917. By setting it to 0.928 or less, film formation becomes easier to stabilize.

[膜的實用特性] 針對本發明之雙軸配向聚丙烯膜所具有的實用特性來說明。 [拉伸斷裂強度] 本發明之雙軸配向聚丙烯膜的長度方向的拉伸斷裂強度的下限較佳為90MPa、更佳為95MPa、進而較佳為100MPa。若為90MPa以上則變得不易產生將印刷墨液轉印時的印刷間距偏差,也易使包裝袋的耐久性優異。長度方向的拉伸斷裂強度的上限就實際的數值而言較佳為200MPa、更佳為190MPa、進而較佳為180MPa。若為200MPa以下則易於減少膜的斷裂和包裝袋的破袋。[Practical properties of membrane] The practical characteristics of the biaxially aligned polypropylene film of the present invention are explained. [Tensile breaking strength] The lower limit of the tensile breaking strength in the longitudinal direction of the biaxially aligned polypropylene film of the present invention is preferably 90 MPa, more preferably 95 MPa, and still more preferably 100 MPa. If it is 90 MPa or more, printing pitch deviation when transferring the printing ink becomes less likely to occur, and the durability of the packaging bag is likely to be excellent. As for the actual numerical value, the upper limit of the tensile breaking strength in the longitudinal direction is preferably 200 MPa, more preferably 190 MPa, and still more preferably 180 MPa. If it is 200 MPa or less, it is easier to reduce film breakage and packaging bag breakage.

本發明之雙軸配向聚丙烯膜的寬度方向的拉伸斷裂強度的下限較佳為320MPa、更佳為340MPa、進而較佳為350MPa。若為320MPa以上則變得不易產生將印刷墨液轉印時的印刷間距偏差,也易使包裝袋的耐久性優異。寬度方向的拉伸斷裂強度的上限就實際的數值而言較佳為500MPa、更佳為480MPa、進而較佳為470MPa。若為500MPa以下則易於減少膜的斷裂和包裝袋的破袋。 拉伸斷裂強度能夠藉由調整延伸倍率、延伸溫度、熱固定溫度而設在範圍內。The lower limit of the tensile breaking strength in the width direction of the biaxially aligned polypropylene film of the present invention is preferably 320 MPa, more preferably 340 MPa, and still more preferably 350 MPa. If it is 320 MPa or more, printing pitch deviation when transferring printing ink becomes less likely to occur, and the durability of the packaging bag is likely to be excellent. As for the actual numerical value, the upper limit of the tensile breaking strength in the width direction is preferably 500 MPa, more preferably 480 MPa, and still more preferably 470 MPa. If it is 500MPa or less, it is easier to reduce film breakage and packaging bag breakage. The tensile breaking strength can be set within a range by adjusting the extension ratio, extension temperature, and heat fixing temperature.

[拉伸斷裂伸度] 本發明之雙軸配向聚丙烯膜的長度方向的拉伸斷裂伸度的下限較佳為50%、更佳為55%、進而較佳為60%。若為50%以上則易於減少膜的斷裂和包裝袋的破袋。長度方向的拉伸斷裂伸度的上限就實際的數值而言較佳為230%、更佳為220%、進而較佳為210%。若為230%以下則變得不易產生將印刷墨液轉印時的印刷間距偏差,也易使包裝袋的耐久性優異。[Tensile elongation at break] The lower limit of the tensile elongation at break in the length direction of the biaxially aligned polypropylene film of the present invention is preferably 50%, more preferably 55%, and still more preferably 60%. If it is more than 50%, it is easy to reduce film breakage and packaging bag breakage. The actual upper limit of the tensile elongation at break in the longitudinal direction is preferably 230%, more preferably 220%, and still more preferably 210%. If it is 230% or less, printing pitch deviation when transferring printing ink becomes less likely to occur, and the durability of the packaging bag is likely to be excellent.

本發明之雙軸配向聚丙烯膜的寬度方向的拉伸斷裂伸度的下限較佳為10%、更佳為15%、進而較佳為17%。若為10%以上,則易於減少膜的斷裂和包裝袋的破袋。寬度方向的拉伸斷裂伸度的上限較佳為60%、更佳為55%、進而較佳為50%。若為60%以下則變得不易產生將印刷墨液轉印時的印刷間距偏差,也易使包裝袋的耐久性優異。 拉伸斷裂伸度能夠藉由調整延伸倍率、延伸溫度、熱固定溫度而設在範圍內。The lower limit of the tensile elongation at break in the width direction of the biaxially aligned polypropylene film of the present invention is preferably 10%, more preferably 15%, and still more preferably 17%. If it is 10% or more, it is easy to reduce film breakage and packaging bag breakage. The upper limit of the tensile elongation at break in the width direction is preferably 60%, more preferably 55%, and still more preferably 50%. If it is 60% or less, printing pitch deviation when transferring printing ink becomes less likely to occur, and the durability of the packaging bag is likely to be excellent. The tensile elongation at break can be set within a range by adjusting the extension ratio, extension temperature, and heat fixing temperature.

[彎曲剛度] 本發明之雙軸配向聚丙烯膜在23℃的長度方向的彎曲剛度的下限較佳為0.3mN・cm、更佳為0.33mN・cm、進而較佳為0.35mN・cm。若為0.3mN・cm以上,則膜能夠薄壁化,且剛性會適於所需的用途。 寬度方向的彎曲剛度的下限較佳為0.5mN・cm、更佳為0.55mN・cm、進而較佳為0.6mN・cm。若為0.5mN・cm以上,則膜能夠薄壁化,且剛性會適於所需的用途。[Bending stiffness] The lower limit of the bending stiffness in the length direction of the biaxially aligned polypropylene film of the present invention at 23° C. is preferably 0.3 mN·cm, more preferably 0.33 mN·cm, and still more preferably 0.35 mN·cm. If it is 0.3mN·cm or more, the film can be made thinner and the rigidity will be suitable for the required use. The lower limit of the bending stiffness in the width direction is preferably 0.5mN·cm, more preferably 0.55mN·cm, and still more preferably 0.6mN·cm. If it is 0.5mN・cm or more, the film can be made thinner and the rigidity will be suitable for the required use.

[環剛度應力] 本發明之雙軸配向聚丙烯膜在23℃的長度方向的環剛度應力S(mN)的下限,若將雙軸配向聚丙烯膜的厚度設為t(μm),較佳為0.00020×t3 、更佳為0.00025×t3 、進而較佳為0.00030×t3 、特佳為0.00035×t3 。若為0.00020×t3 以上,則易於保持包裝體的形狀。在23℃的長度方向的環剛度應力S(mN)的上限較佳為0.00080×t3 、更佳為0.00075×t3 、進而較佳為0.00072×t3 、特佳為0.00070×t3 。若為0.00080×t3 以下,則易於實際地製造。 本發明之雙軸配向聚丙烯膜在23℃的寬度方向的環剛度應力S(mN)的下限,若將雙軸配向聚丙烯膜的厚度設為t(μm),較佳為0.0010×t3 、更佳為0.0011×t3 、進而較佳為0.0012×t3 、特佳為0.0013×t3 。若為0.0010×t3 以上,則易於保持包裝體的形狀。在23℃的寬度方向的環剛度應力S(mN)的上限較佳為0.0020×t3 、更佳為0.0019×t3 、進而較佳為0.0018×t3 、特佳為0.0017×t3 。若為0.0020×t3 以下,則易於實際地製造。[Ring Stiffness Stress] The lower limit of the ring stiffness stress S (mN) in the length direction of the biaxially aligned polypropylene film of the present invention at 23°C is preferably set to t (μm) when the thickness of the biaxially aligned polypropylene film is It is 0.00020×t 3 , more preferably 0.00025×t 3 , further preferably 0.00030×t 3 , and particularly preferably 0.00035×t 3 . If it is 0.00020×t 3 or more, the shape of the package can be easily maintained. The upper limit of the ring stiffness stress S (mN) in the length direction at 23° C. is preferably 0.00080×t 3 , more preferably 0.00075×t 3 , further preferably 0.00072×t 3 , and particularly preferably 0.00070×t 3 . If it is 0.00080×t 3 or less, actual production will be easy. The lower limit of the ring stiffness stress S (mN) in the width direction of the biaxially aligned polypropylene film of the present invention at 23°C is preferably 0.0010 × t 3 if the thickness of the biaxially aligned polypropylene film is t (μm). , more preferably 0.0011×t 3 , further preferably 0.0012×t 3 , and particularly preferably 0.0013×t 3 . If it is 0.0010×t 3 or more, the shape of the package can be easily maintained. The upper limit of the ring stiffness stress S (mN) in the width direction at 23° C. is preferably 0.0020×t 3 , more preferably 0.0019×t 3 , further preferably 0.0018×t 3 , and particularly preferably 0.0017×t 3 . If it is 0.0020×t 3 or less, actual production will be easy.

環剛度應力雖然是表示膜的硬挺度的指標,但環剛度應力也取決於膜的厚度。環剛度應力的測定方法如同以下所述。將膜的長度方向作為長條的長軸(環方向),或將膜的寬度方向作為長條的長軸(環方向),分別切出2片110mm×25.4mm的長條。以夾子夾著這些長條,就長條的長軸成為膜的長度方向及寬度方向者來製作成膜的其中一面成為環的內面之測定用環、與該面的相反面成為環的內面之測定用環。將長條的長軸成為膜的長度方向之測定用的環,以寬度方向垂直於東洋精機股份有限公司製造的LOOP STIFFNESS TESTER DA的夾具部的狀態來安裝,鬆開夾子,以夾具間隔設為50mm、推入深度設為15mm、壓縮速度設為3.3mm/秒來測定環剛度應力。 測定是將膜的其中一面以成為環的內面的方式而成之環的環剛度應力與厚度測定5次,之後另一面以成為環的內面的方式而成之環也測定5次。使用這總計10次的數據,以各試驗片的厚度(μm)的3次方為橫軸,將該環剛度應力(mN)作為縱軸來作圖,並以截距為0的直線來逼近,求得該斜率a。斜率a意謂一種膜固有的特性値,該特性值並不隨決定剛性的厚度而異。將斜率a作為硬挺度的評價値。長條的長軸成為膜的寬度方向之測定用的環亦同樣地測定。Although the ring stiffness stress is an index indicating the stiffness of the film, the ring stiffness stress also depends on the thickness of the film. The ring stiffness stress is measured as follows. Using the length direction of the film as the long axis of the strip (circular direction) or the width direction of the film as the long axis of the strip (circular direction), cut out two strips of 110 mm x 25.4 mm respectively. Hold these long strips with a clip, and make a measurement ring in which one side of the film becomes the inner surface of the ring, and the opposite side of the film becomes the inner surface of the ring so that the long axis of the long axis becomes the length direction and width direction of the film. Ring for measuring surface. The long axis of the long strip was used as a ring for measuring the length direction of the film, and the width direction was perpendicular to the clamp part of the LOOP STIFFNESS TESTER DA manufactured by Toyo Seiki Co., Ltd., and the clamp was loosened and the clamp interval was set to 50mm, the pushing depth is set to 15mm, and the compression speed is set to 3.3mm/second to measure the ring stiffness stress. The measurement was performed by measuring the ring stiffness stress and thickness of the ring with one side of the film forming the inner surface of the ring five times, and then measuring the ring stiffness stress and thickness of the ring with the other surface forming the inner surface of the ring five times. Using the data from a total of 10 times, a graph was drawn with the cubic thickness of each test piece (μm) as the horizontal axis and the ring stiffness stress (mN) as the vertical axis, and was approximated by a straight line with an intercept of 0 , find the slope a. The slope a means a characteristic value inherent to the film that does not vary with the thickness that determines rigidity. Let the slope a be the evaluation value of the stiffness. The long axis of the strip serves as a measurement ring in the width direction of the film and is measured in the same manner.

[熱封時的皺褶] 為了形成包裝食品之袋,對製袋完成之袋填充內容物,進行加熱將膜熔融而熔接並密封。又,在一邊填充食品一邊製袋時多為亦同樣地進行的情況。通常是在基材膜積層由聚乙烯或聚丙烯等所構成的密封劑膜,並使此密封劑膜面彼此熔接。加熱方法是從基材膜側以加熱板施以壓力將膜壓住來密封,而密封寬度多是設為10mm左右的情況。此時由於基材膜亦被加熱,此時的收縮會使得皺褶發生。在袋的耐久性中,皺褶較少為佳,而為了提高購買意願也是皺褶較少為佳。密封溫度雖然也有在120℃左右的情況,但為了提高製袋加工速度而要求於更高溫的密封溫度,較佳為即使在那種情況收縮仍小。在對袋的開口部熔接夾鏈的情況,要求在更高溫的密封。[Wrinkles during heat sealing] In order to form a bag for packaging food, the finished bag is filled with contents, heated to melt the film, welded and sealed. Moreover, when making a bag while filling food, it is often done similarly. Usually, a sealant film made of polyethylene, polypropylene, etc. is laminated on a base film, and the surfaces of the sealant films are welded to each other. The heating method is to apply pressure from the base film side with a heating plate to press the film to seal, and the sealing width is often set to about 10 mm. At this time, since the base film is also heated, the shrinkage at this time will cause wrinkles. In terms of the durability of the bag, it is better to have fewer wrinkles, and in order to increase purchase intention, it is also better to have fewer wrinkles. Although the sealing temperature may be around 120°C, in order to increase the bag-making processing speed, a higher sealing temperature is required, and it is preferable that the shrinkage is small even in that case. When the clip chain is welded to the opening of the bag, sealing at a higher temperature is required.

[印刷間距偏差] 作為包裝膜的構成,就基本的構成而言,多為由被施以印刷的基材膜與密封劑膜之積層膜所構成的情況。就袋的製造而言,會使用製袋機,有三邊封袋、站立袋、夾邊袋等,而使用各式各樣的製袋機。印刷間距偏差認為是由於在印刷步驟時對膜施加張力或熱,導致膜的基材伸縮的緣故而發生。避免印刷間距偏差導致的瑕疵品在資源的有效活用這一點係為重要,對於為了提高購買意願也很重要。[Printing pitch deviation] As for the structure of the packaging film, in terms of its basic structure, it is often composed of a laminated film of a printed base film and a sealant film. As far as the manufacturing of bags is concerned, bag making machines are used, including three-side sealing bags, stand-up bags, side-clip bags, etc., and various bag making machines are used. The printing pitch deviation is considered to occur because tension or heat is applied to the film during the printing step, causing the base material of the film to expand and contract. It is important to effectively use resources to avoid defective products caused by printing pitch deviation, and it is also important to increase purchase intention.

[膜加工] 本發明之雙軸配向聚丙烯膜的印刷能夠依用途,藉由凸版印刷、平版印刷、凹版印刷、網版印刷、轉印印刷方式來進行。 又,也能夠將由低密度聚乙烯、線狀低密度聚乙烯、乙烯-乙酸乙烯酯共聚物、聚丙烯、聚酯所構成的未延伸片、單軸延伸膜、雙軸延伸膜作為密封劑膜來貼合,而作為經賦予熱封性之層合體來使用。欲進一步提高氣體阻隔性或耐熱性時,能夠將由鋁箔或聚偏二氯乙烯、尼龍、乙烯-乙烯醇共聚物、聚乙烯醇所構成的未延伸片、單軸延伸膜、雙軸延伸膜設在雙軸配向聚丙烯膜與密封劑膜之間作為中間層。就密封劑膜的貼合而言,能夠使用藉由乾式層合法或熱熔層合法所塗佈而成的接著劑。 就提高氣體阻隔性而言,亦能夠對雙軸配向聚丙烯膜和中間層膜、或者密封劑膜將鋁或無機氧化物進行蒸鍍加工。就蒸鍍方法而言能夠採用真空蒸鍍、濺鍍、離子鍍覆法,尤其較佳為將二氧化矽、鋁氧、或這些的混合物進行真空蒸鍍。 對於本發明之雙軸配向聚丙烯膜,例如,藉由將多元醇的脂肪酸酯類、高級脂肪酸的胺類、高級脂肪酸的醯胺類、高級脂肪酸的胺或醯胺的環氧乙烷加成物等之防霧劑在膜中的存在量設為0.2質量%至5質量%的範圍,能夠作為適於包裝由蔬菜、水果、花草等要求高鮮度的植物類所構成的生鮮品之雙軸配向聚丙烯膜。 又,只要在不損及本發明之效果的範圍,亦能調配用以提升平滑性或抗靜電性等之品質的各種添加劑,例如,用以提升生產性而調配蠟、金屬皂等之潤滑劑、塑化劑、加工助劑或熱穩定劑、抗氧化劑、抗靜電劑、紫外線吸收劑等。[Film processing] The biaxially aligned polypropylene film of the present invention can be printed by letterpress printing, offset printing, gravure printing, screen printing, or transfer printing according to the purpose. Furthermore, an unstretched sheet, a uniaxially stretched film, or a biaxially stretched film made of low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, or polyester can also be used as the sealant film. It is used as a laminate with heat sealability imparted to it. To further improve gas barrier properties or heat resistance, unstretched sheets, uniaxially stretched films, or biaxially stretched films made of aluminum foil, polyvinylidene chloride, nylon, ethylene-vinyl alcohol copolymer, or polyvinyl alcohol can be used. As an intermediate layer between biaxially oriented polypropylene film and sealant film. For the lamination of the sealant film, an adhesive applied by a dry lamination method or a hot melt lamination method can be used. In order to improve the gas barrier properties, the biaxially aligned polypropylene film, the interlayer film, or the sealant film can also be vapor-deposited with aluminum or inorganic oxide. As the evaporation method, vacuum evaporation, sputtering, and ion plating can be used, and vacuum evaporation of silicon dioxide, aluminum oxide, or a mixture thereof is particularly preferred. For the biaxially aligned polypropylene film of the present invention, for example, by adding fatty acid esters of polyols, amines of higher fatty acids, amide of higher fatty acids, amines of higher fatty acids or amide ethylene oxide The amount of the anti-fogging agent present in the film is set to be in the range of 0.2% by mass to 5% by mass, and it can be used as a double axis suitable for packaging fresh products composed of vegetables, fruits, flowers and other plants that require high freshness. Oriented polypropylene film. In addition, as long as the effects of the present invention are not impaired, various additives for improving smoothness, antistatic properties, etc. can also be blended. For example, lubricants such as waxes and metallic soaps can be blended to improve productivity. , plasticizers, processing aids or heat stabilizers, antioxidants, antistatic agents, UV absorbers, etc.

[產業可利用性] 本發明之雙軸配向聚丙烯膜由於具有如上述般在以往所沒有的優異特性,因此能夠較佳地使用於包裝袋,而且也能夠將膜的厚度變得比以往薄。 並且,也適合於電容器或馬達等的絕緣膜、太陽能電池的背板、無機氧化物的阻隔膜、ITO(Indium Tin Oxide;氧化銦錫)等之透明導電膜的基膜等在高溫使用的用途、或分離膜等需要剛性的用途。又,使用在以往難以使用的塗佈劑或墨液、層合接著劑等,變得能夠在高溫塗佈或印刷加工,能夠期待生產的效率化。 [實施例][Industrial Availability] Since the biaxially aligned polypropylene film of the present invention has excellent characteristics not seen in the past as described above, it can be preferably used in packaging bags, and the thickness of the film can also be made thinner than before. In addition, it is also suitable for use in high-temperature applications such as insulating films for capacitors and motors, backsheets for solar cells, barrier films of inorganic oxides, and base films of transparent conductive films such as ITO (Indium Tin Oxide). , or separation membranes and other applications that require rigidity. In addition, by using coating agents, inks, lamination adhesives, etc. that have been difficult to use in the past, high-temperature coating or printing processing can be used, and production efficiency can be expected to be improved. [Example]

以下,藉由實施例來詳細地說明本發明。另外,特性是藉由以下的方法來進行測定、評價。 (1)熔體流動速率 熔體流動速率(MFR)是遵循JIS K 7210,以溫度230℃、荷重2.16kgf來測定。Hereinafter, the present invention will be described in detail through examples. In addition, the characteristics are measured and evaluated by the following methods. (1) Melt flow rate The melt flow rate (MFR) is measured in accordance with JIS K 7210 at a temperature of 230°C and a load of 2.16kgf.

(2)內消旋五單元組分率 聚丙烯樹脂的內消旋五單元組分率([mmmm]%)之測定是使用13 C-NMR來進行。內消旋五單元組分率是依照Zambelli等人於Macromolecules,第6巻,925頁(1973)所記載的方法來算出。13 C-NMR測定是使用BRUKER公司製造的AVANCE500,將試料200mg以135℃溶解在鄰二氯苯與氘代苯的8:2之混合液,並於110℃進行。(2) Meso-pentad ratio The meso-pentad ratio ([mmmm]%) of the polypropylene resin is measured using 13 C-NMR. The meso pentad fraction is calculated according to the method described by Zambelli et al., Macromolecules, Vol. 6, p. 925 (1973). 13 C-NMR measurement was performed using AVANCE 500 manufactured by BRUKER. 200 mg of the sample was dissolved in an 8:2 mixture of o-dichlorobenzene and deuterated benzene at 135°C, and was performed at 110°C.

(3)聚丙烯樹脂的數平均分子量、重量平均分子量、分子量10萬以下之成分量、及分子量分布 使用凝膠滲透層析法(GPC),設定為單分散聚苯乙烯基準,以PP(Polypropylene;聚丙烯)換算分子量來求出。基線不明確時,係以至最接近標準物質的溶析峰之高分子量側的溶析峰的高分子量側的山腳的最低位置為止之範圍來設定為基線。 GPC測定條件如下。 裝置:HLC-8321PC/HT(Tosoh股份有限公司製造) 偵測器:RI(Refractive Index;折射率) 溶劑:1,2,4-三氯苯+二丁基羥基甲苯(0.05%) 管柱:TSKgelguardcolumnHHR(30)HT(7.5mmI.D.×7.5cm)×1支+ TSKgelGMHHR-H(20)HT(7.8mmI.D.×30cm)×3支 流量:1.0mL/min 注入量:0.3mL 測定溫度:140℃ 數平均分子量(Mn)、質量平均分子量(Mw)是分別依據經由分子量校正曲線所獲得之GPC曲線的各溶析位置的分子量(Mi)之分子數(Ni )並以下式來定義。 數平均分子量:Mn=Σ(Ni ・Mi )/ΣNi 質量平均分子量:Mw=Σ(Ni ・Mi 2 )/Σ(Ni ・Mi ) 在此,分子量分布能夠以Mw/Mn來獲得。 而且,由在GPC所獲得的分子量分布的積分曲線,求得分子量10萬以下之成分的比例。(3) The number average molecular weight, weight average molecular weight, component weight with a molecular weight of less than 100,000, and molecular weight distribution of the polypropylene resin were set to monodisperse polystyrene standards using gel permeation chromatography (GPC), and PP (Polypropylene ; polypropylene) and calculated by converting the molecular weight. When the baseline is unclear, the range up to the lowest position of the foot of the high molecular weight side of the elution peak closest to the high molecular weight side of the elution peak of the standard substance is set as the baseline. GPC measurement conditions are as follows. Device: HLC-8321PC/HT (manufactured by Tosoh Co., Ltd.) Detector: RI (Refractive Index; refractive index) Solvent: 1,2,4-trichlorobenzene + dibutylated hydroxytoluene (0.05%) Column: TSKgelguardcolumnHHR (30)HT (7.5mmI.D. Temperature: 140°C Number average molecular weight (Mn) and mass average molecular weight (Mw) are based on the number of molecules (N i ) of the molecular weight (Mi) of each dissolution position of the GPC curve obtained through the molecular weight calibration curve and are calculated by the following formula definition. Number average molecular weight: Mn=Σ(N i・M i )/ΣNi Mass average molecular weight: Mw=Σ(N i・M i 2 )/Σ(N i・M i ) Here, the molecular weight distribution can be expressed as Mw/Mn to get. Furthermore, from the integral curve of the molecular weight distribution obtained by GPC, the proportion of components with a molecular weight of 100,000 or less is determined.

(4)結晶化溫度(Tc)、熔化溫度(Tm) 使用TA Instruments公司製造的Q1000差示掃描型熱量計,在氮氣氛圍下進行熱測定。從聚丙烯樹脂的丸粒切出約5mg並封入測定用的鋁盤。昇溫至230℃保持5分鐘後,以-10℃/分鐘的速度冷卻至30℃,將放熱峰溫度作為結晶化溫度(Tc)。又,結晶化熱量(ΔHc)是將放熱峰的面積以平滑地連接自波峰的開始到波峰結束的方式來設定基線而求得。維持原樣在30℃保持5分鐘,以10℃/分鐘昇溫至230℃,將主要的吸熱峰溫度作為熔化溫度(Tm)。(4) Crystallization temperature (Tc), melting temperature (Tm) Thermal measurement was performed in a nitrogen atmosphere using a Q1000 differential scanning calorimeter manufactured by TA Instruments. Approximately 5 mg was cut out from the polypropylene resin pellets and sealed in an aluminum pan for measurement. After raising the temperature to 230°C and holding it for 5 minutes, it was cooled to 30°C at a rate of -10°C/min, and the exothermic peak temperature was taken as the crystallization temperature (Tc). In addition, the crystallization heat amount (ΔHc) was obtained by setting a baseline so that the area of the exothermic peak smoothly connects from the beginning of the peak to the end of the peak. The temperature was maintained at 30° C. for 5 minutes, and the temperature was raised to 230° C. at 10° C./min. The main endothermic peak temperature was taken as the melting temperature (Tm).

(5)膜厚度 使用Seiko EM公司製造的Millitron 1202D來測量膜的厚度。(5)Film thickness The film thickness was measured using Millitron 1202D manufactured by Seiko EM Corporation.

(6)霧度 使用日本電色工業股份有限公司製造的NDH5000,在23℃依照JISK7105來測定。(6)Haze NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. was used, and it was measured in accordance with JISK7105 at 23°C.

(7)熱機械分析(TMA;Thermomechanical Analysis) 使用島津製作所製造的熱機械分析裝置TMA-60,以夾具間隔10mm設置寬度4mm的膜樣品,並以測定荷重40g且以20℃/分鐘自30℃昇溫至180℃來測定至150℃為止的最大伸長量。(7) Thermomechanical Analysis (TMA; Thermomechanical Analysis) Using a thermomechanical analysis device TMA-60 manufactured by Shimadzu Corporation, a film sample with a width of 4 mm was set at a clamp interval of 10 mm, and the maximum temperature up to 150°C was measured with a measurement load of 40g and a temperature increase from 30°C to 180°C at 20°C/min. Elongation.

(8)拉伸試驗 遵循JIS K 7127在23℃測定膜的長度方向及寬度方向的拉伸強度。樣品是從膜切出15mm×200mm的尺寸,夾具寬度以100mm裝設於拉伸試驗機(Instron Japan Co. Ltd.製造的Dual Column桌上型試驗機Instron 5965)。以拉伸速度200mm/分鐘進行拉伸試驗。從獲得的應變-應力曲線,並自伸長初期之直線部份的斜率來求出楊氏模數、及5%伸長時的應力(F5)。拉伸斷裂強度、拉伸斷裂伸度分別是樣品在斷裂的時點的強度與伸度。 藉由在80℃的恆溫槽中進行測定,求得在80℃的楊氏模數與F5。另外,測定是將夾具裝設在預先設定於80℃的恆溫槽中,到測定樣品為止從安裝起保持1分鐘來進行。(8) Tensile test The tensile strength of the film in the length direction and width direction was measured at 23°C in accordance with JIS K 7127. The sample was cut out from the film to a size of 15 mm×200 mm, and was mounted on a tensile testing machine (Dual Column desktop testing machine Instron 5965 manufactured by Instron Japan Co. Ltd.) with a clamp width of 100 mm. The tensile test was performed at a tensile speed of 200 mm/min. From the obtained strain-stress curve and the slope of the straight line from the initial stage of elongation, the Young's modulus and the stress at 5% elongation (F5) are calculated. Tensile breaking strength and tensile breaking elongation are respectively the strength and elongation of the sample at the point of rupture. By measuring in a constant temperature bath at 80°C, the Young's modulus and F5 at 80°C were obtained. In addition, the measurement was performed by installing the jig in a constant temperature bath preset at 80° C. and holding it for 1 minute from the time of installation until the sample was measured.

(9)熱收縮率 遵循JIS Z 1712用以下的方法來測定。將膜以20mm寬度及以200mm的長度分別朝膜的長度方向、寬度方向切下,吊在120℃或150℃的熱風烘箱中加熱5分鐘。測定加熱後的長度,以收縮的長度相對於原本的長度之比例求得熱收縮率。(9)Thermal shrinkage rate It is measured by the following method in accordance with JIS Z 1712. Cut the film into length and width directions of 20 mm and 200 mm, respectively, and hang it in a hot air oven at 120°C or 150°C for 5 minutes. The length after heating is measured, and the thermal shrinkage rate is calculated as the ratio of the shrunk length to the original length.

(10)折射率、ΔNy、面配向係數 使用股份有限公司ATAGO製造的阿貝折射計並以波長589.3nm、溫度23℃來測定。將沿著膜的長度方向、寬度方向的折射率分別設為Nx、Ny,將厚度方向的折射率設為Nz。ΔNy是使用Nx、Ny、Nz,並使用(式)Ny-[(Nx+Nz)/2]來求得。又,面配向係數(ΔP)是使用(式)[(Nx+Ny)/2]-Nz來計算。(10)Refractive index, ΔNy, plane alignment coefficient An Abbe refractometer manufactured by ATAGO Co., Ltd. was used and measured at a wavelength of 589.3 nm and a temperature of 23°C. Let the refractive index along the length direction and width direction of the film be Nx and Ny respectively, and let the refractive index in the thickness direction be Nz. ΔNy is obtained using Nx, Ny, and Nz, and using (formula) Ny-[(Nx+Nz)/2]. In addition, the plane alignment coefficient (ΔP) is calculated using (formula) [(Nx+Ny)/2]-Nz.

(11)X射線半值寬度、配向度 使用X射線繞射裝置(股份有限公司Rigaku製造的RINT2500),以透射法來測定。使用波長1.5418Å的X射線,偵測器是使用閃爍計數器。以成為500μm的厚度的方式使膜疊合並調配成試料。在聚丙烯樹脂的α型結晶之(110)面的繞射峰位置(繞射角度2θ=14.1°)放置試料台,將樣品以膜的厚度方向為軸使之旋轉360°,獲得(110)面的繞射強度的方位角相依性。由此方位角相依性,求出源自膜的寬度方向的配向結晶之繞射峰的半值寬度Wh。 又,使用Wh並由下述式算出X射線配向度。 X射線配向度=(180-Wh)/180(11) X-ray half value width, alignment degree It measured by the transmission method using an X-ray diffraction device (RINT2500 manufactured by Rigaku Co., Ltd.). X-rays with a wavelength of 1.5418Å are used, and the detector uses a scintillation counter. The films were stacked so as to have a thickness of 500 μm and prepared into a sample. Place the sample stage at the diffraction peak position (diffraction angle 2θ = 14.1°) of the (110) plane of the α-type crystal of the polypropylene resin, rotate the sample 360° with the thickness direction of the film as the axis, and obtain (110) Azimuth dependence of the diffraction intensity of the surface. From this azimuth angle dependence, the half-value width Wh of the diffraction peak originating from the aligned crystals in the width direction of the film was determined. Furthermore, the X-ray alignment degree was calculated from the following equation using Wh. X-ray alignment degree=(180-Wh)/180

(12)彎曲剛度、垂下量 遵循JIS L 1096B法(滑動法),藉由以下的順序來求得。製作20mm×150mm的試驗片,使試驗機本體與移動台的上面一致之後,在試驗機之台以突出50mm的方式放上試驗片並設置砝碼。然後,輕輕地轉動把手使試料台下降,測定試料的自由端在離開試料台之時點的垂下量(δ)。使用此垂下量δ與膜厚度、試驗片尺寸、膜密度0.91g/cm3 ,藉由以下的算式求得彎曲剛度(Br)。 Br=WL4 /8δ Br:彎曲剛度(mN・cm) W:試驗片的每單位面積重力(mN/cm2 ) L:試驗片的長度(cm) δ:垂下量(cm)(12) The bending stiffness and sag amount are obtained by following the JIS L 1096B method (sliding method). Make a test piece of 20 mm x 150 mm and align the testing machine body with the top of the moving table. Place the test piece on the testing machine table with a protrusion of 50 mm and set the weight. Then, gently turn the handle to lower the sample table, and measure the hanging amount (δ) of the free end of the sample when it leaves the sample table. Using this sag amount δ, the film thickness, the test piece size, and the film density of 0.91 g/cm 3 , the bending stiffness (Br) was obtained by the following equation. Br=WL 4 /8δ Br: Bending stiffness (mN・cm) W: Gravity per unit area of the test piece (mN/cm 2 ) L: Length of the test piece (cm) δ: Droop amount (cm)

(13)環剛度應力、硬挺度 將膜的長度方向作為長條的長軸(環方向),或將膜的寬度方向作為長條的長軸(環方向),分別切出10片110mm×25.4mm的長條狀試驗片。以夾子夾著這些長條狀試驗片,就長條的長軸成為膜的長度方向及寬度方向者來製作成膜的其中一面成為環的內面之測定用環、與該面的相反面成為環的內面之測定用環。將長條的長軸成為膜的長度方向之測定用的環,以寬度方向垂直於股份有限公司東洋精機製作所製造的LOOP STIFFNESS TESTER DA的夾具部的狀態來安裝,鬆開夾子,以夾具間隔設為50mm、推入深度設為15mm、壓縮速度設為3.3mm/秒來測定環剛度應力。 測定是將膜的其中一面以成為環的內面的方式而成之環的環剛度應力與厚度測定5次,之後另一面以成為環的內面的方式而成之環也測定5次。使用這總計10次的數據,以各試驗片的厚度(μm)的3次方為橫軸,將該環剛度應力(mN)作為縱軸來作圖,並以截距為0的直線來逼近,求得該斜率a。將斜率a作為硬挺度的評價値。長條的長軸成為膜的寬度方向之測定用的環亦同樣地測定。(13) Ring stiffness stress, stiffness Using the longitudinal direction of the film as the long axis of the strip (circular direction) or the width direction of the film as the long axis of the strip (circular direction), 10 strip-shaped test pieces of 110 mm×25.4 mm were cut out. These elongated test pieces were sandwiched with a clip, and a measurement ring was produced in which one side of the film became the inner surface of the ring, with the long axis of the long axis becoming the length direction and the width direction of the film, and the opposite side to this surface became the inner surface of the ring. A ring for measuring the inner surface of a ring. The long axis of the strip is used as a ring for measuring the length direction of the film, and the width direction is perpendicular to the clamp part of the LOOP STIFFNESS TESTER DA manufactured by Toyo Seiki Seisakusho Co., Ltd., and the clamp is loosened and placed at intervals between the clamps. The ring stiffness stress is measured by setting the pushing depth to 15mm, the pushing depth to 50mm, and the compression speed to 3.3mm/second. The measurement was performed by measuring the ring stiffness stress and thickness of the ring with one side of the film forming the inner surface of the ring five times, and then measuring the ring stiffness stress and thickness of the ring with the other surface forming the inner surface of the ring five times. Using the data from a total of 10 times, a graph was drawn with the cubic thickness of each test piece (μm) as the horizontal axis and the ring stiffness stress (mN) as the vertical axis, and was approximated by a straight line with an intercept of 0 , find the slope a. Let the slope a be the evaluation value of the stiffness. The long axis of the strip serves as a measurement ring in the width direction of the film and is measured in the same manner.

[實施例1] 作為聚丙烯樹脂,是使用了MFR=7.5g/10分鐘、Tc=116.2℃、Tm=162.5℃之丙烯同元聚合物PP-1(住友化學股份有限公司製造,Sumitomo Noblen FLX80E4)。在250℃自T字模擠壓成片狀,使之接觸20℃的冷卻輥,並直接投入20℃的水槽。之後,在145℃以兩對的輥朝長度方向延伸4.5倍,接著以夾子夾住兩端,引導至熱風烘箱中,在170℃預熱後,藉由朝寬度方向在160℃延伸6倍作為第1段,接下來在145℃延伸1.36倍作為第2段,進行合計8.2倍的延伸。在寬度方向延伸隨後,維持把持於夾子在100℃冷卻,之後在163℃進行熱固定。這樣獲得的膜的厚度為18.7μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件。該膜的物性,如同於表3所示,獲得了剛性高、在高溫的熱收縮率低的膜。[Example 1] As the polypropylene resin, propylene homopolymer PP-1 (Sumitomo Noblen FLX80E4, manufactured by Sumitomo Chemical Co., Ltd.) with MFR=7.5g/10 minutes, Tc=116.2°C, and Tm=162.5°C was used. The sheet is extruded from a T-die at 250°C, contacted with a cooling roll at 20°C, and directly put into a water tank at 20°C. Then, extend it 4.5 times in the length direction with two pairs of rollers at 145°C, then clamp both ends with clips, guide it to a hot air oven, preheat at 170°C, and extend it 6 times in the width direction at 160°C. The first step is then extended 1.36 times at 145°C as the second step, and a total extension of 8.2 times is performed. After extending in the width direction, it was cooled at 100°C while being held by a clip, and then heat-set at 163°C. The thickness of the film thus obtained was 18.7 μm. Table 1 shows the structure of the polypropylene resin, and Table 2 shows the film forming conditions. The physical properties of this film are as shown in Table 3. A film with high rigidity and low thermal shrinkage at high temperatures was obtained.

[實施例2] 作為聚丙烯樹脂,是摻合了80重量份的PP-1與20重量份的MFR=11g/10分鐘、[mmmm]=98.8%、Tc=116.5℃、Tm=161.5℃之丙烯同元聚合物PP-2(住友化學股份有限公司製造,EL80F5)來使用。除了將長度方向的延伸溫度設為142℃,將寬度方向的第1段的延伸溫度設為162℃,將熱固定溫度設為165℃以外都與實施例1同樣地進行。獲得的膜的厚度為21.3μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件。該膜的物性,如同於表3所示,獲得了剛性高、且在高溫的熱收縮率低的膜。[Example 2] The polypropylene resin is a propylene homopolymer that contains 80 parts by weight of PP-1 and 20 parts by weight of MFR=11g/10 minutes, [mmmm]=98.8%, Tc=116.5°C, and Tm=161.5°C. PP-2 (manufactured by Sumitomo Chemical Co., Ltd., EL80F5) was used. The process was carried out in the same manner as in Example 1 except that the stretching temperature in the longitudinal direction was 142°C, the stretching temperature in the first step in the width direction was 162°C, and the heat fixing temperature was 165°C. The thickness of the film obtained was 21.3 μm. Table 1 shows the structure of the polypropylene resin, and Table 2 shows the film forming conditions. The physical properties of this film are as shown in Table 3. A film with high rigidity and low thermal shrinkage at high temperatures was obtained.

[實施例3] 除了在熱固定時施以3%的弛緩以外,都與實施例2同樣地進行。獲得的膜的厚度為21.1μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件。 該膜的物性,如同於表3所示,獲得了剛性高、且在高溫的熱收縮率低的膜。[Example 3] The procedure was carried out in the same manner as in Example 2 except that 3% relaxation was provided during heat fixation. The thickness of the film obtained was 21.1 μm. Table 1 shows the structure of the polypropylene resin, and Table 2 shows the film forming conditions. The physical properties of this film are as shown in Table 3. A film with high rigidity and low thermal shrinkage at high temperatures was obtained.

[實施例4] 除了將長度方向的延伸溫度設為145℃,將寬度方向的延伸隨後的冷卻溫度設為140℃以外,都與實施例2同樣地進行。獲得的膜的厚度為18.9μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件。該膜的物性,如同於表3所示,獲得了剛性高的膜。[Example 4] The process was carried out in the same manner as in Example 2 except that the stretching temperature in the longitudinal direction was 145°C and the cooling temperature after stretching in the width direction was 140°C. The thickness of the film obtained was 18.9 μm. Table 1 shows the structure of the polypropylene resin, and Table 2 shows the film forming conditions. The physical properties of this film are as shown in Table 3, and a film with high rigidity was obtained.

[實施例5] 除了在寬度方向延伸後不冷卻,而維持把持於夾子,在165℃進行熱固定以外,都與實施例2同樣地進行。獲得的膜的厚度為19.5μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件。該膜的物性,如同於表3所示,獲得了剛性高、且在高溫的熱收縮率低的膜。[Example 5] The procedure was carried out in the same manner as in Example 2 except that it was not cooled after stretching in the width direction, but was held by the clip and heat-fixed at 165°C. The thickness of the film obtained was 19.5 μm. Table 1 shows the structure of the polypropylene resin, and Table 2 shows the film forming conditions. The physical properties of this film are as shown in Table 3. A film with high rigidity and low thermal shrinkage at high temperatures was obtained.

[實施例6] 除了將寬度方向的第2段的延伸溫度設為155℃以外,都與實施例2同樣地進行。這樣獲得的膜的厚度為20.3μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件。該膜的物性,如同於表3所示,獲得了剛性高、且在高溫的熱收縮率低的膜。[Example 6] The process was carried out in the same manner as in Example 2 except that the stretching temperature in the second step in the width direction was 155°C. The thickness of the film thus obtained was 20.3 μm. Table 1 shows the structure of the polypropylene resin, and Table 2 shows the film forming conditions. The physical properties of this film are as shown in Table 3. A film with high rigidity and low thermal shrinkage at high temperatures was obtained.

[實施例7] 除了將長度方向延伸倍率設為4.8倍以外,都與實施例2同樣地進行。獲得的膜的厚度為19.1μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件。該膜的物性,如同於表3所示,獲得了剛性高、且在高溫的熱收縮率低的膜。[Example 7] The procedure was carried out in the same manner as in Example 2 except that the longitudinal stretching ratio was set to 4.8 times. The thickness of the film obtained was 19.1 μm. Table 1 shows the structure of the polypropylene resin, and Table 2 shows the film forming conditions. The physical properties of this film are as shown in Table 3. A film with high rigidity and low thermal shrinkage at high temperatures was obtained.

[實施例8] 除了在寬度方向延伸中,將第1段的延伸倍率設為6.6倍,將第2段的延伸倍率設為1.5倍,合計為9.9倍的延伸以外,都與實施例2同樣地進行。獲得的膜的厚度為20.1μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件。該膜的物性,如同於表3所示,獲得了剛性高、且在高溫的熱收縮率低的膜。[Example 8] In the width direction stretching, the same procedure as in Example 2 was performed except that the stretching ratio in the first step was set to 6.6 times and the stretching ratio in the second step was set to 1.5 times, resulting in a total stretching of 9.9 times. The thickness of the film obtained was 20.1 μm. Table 1 shows the structure of the polypropylene resin, and Table 2 shows the film forming conditions. The physical properties of this film are as shown in Table 3. A film with high rigidity and low thermal shrinkage at high temperatures was obtained.

[比較例1] 使用PP-1作為聚丙烯樹脂,在250℃自T字模擠壓成片狀,使之接觸20℃的冷卻輥,並直接投入20℃的水槽。之後,在143℃進行4.5倍的長度方向延伸,將在拉幅機中之寬度方向延伸時的預熱溫度設為170℃,將延伸溫度設為158℃來進行8.2倍延伸,接著在168℃進行熱固定。獲得的膜的厚度為18.6μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件,於表3顯示物性。該膜的物性,如同於表3所示,係剛性較低。[Comparative example 1] Use PP-1 as polypropylene resin, extrudate it into a sheet form from a T-die at 250°C, make it contact with a cooling roller at 20°C, and put it directly into a water tank at 20°C. After that, 4.5 times of lengthwise extension was performed at 143°C, the preheating temperature during widthwise extension in the tenter was set to 170°C, and the stretching temperature was set to 158°C to extend 8.2 times, and then at 168°C Perform heat fixation. The thickness of the film obtained was 18.6 μm. Table 1 shows the structure of the polypropylene resin, Table 2 shows the film forming conditions, and Table 3 shows the physical properties. The physical properties of this film, as shown in Table 3, are low rigidity.

[比較例2] 除了作為聚丙烯樹脂,是摻合了80重量份的PP-1與20重量份的PP-2來使用以外,都與比較例1同樣地進行。獲得的膜的厚度為20.0μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件,於表3顯示物性。該膜的物性,如同於表3所示,係剛性較低。[Comparative example 2] The same procedure as Comparative Example 1 was performed except that 80 parts by weight of PP-1 and 20 parts by weight of PP-2 were blended as the polypropylene resin. The thickness of the film obtained was 20.0 μm. Table 1 shows the structure of the polypropylene resin, Table 2 shows the film forming conditions, and Table 3 shows the physical properties. The physical properties of this film, as shown in Table 3, are low rigidity.

[比較例3] 作為聚丙烯樹脂,是使用了MFR=3g/10分鐘、Tc=117.2℃、Tm=160.6℃之PP-3(日本聚丙烯股份有限公司製造,FL203D)。在250℃自T字模擠壓成片狀,使之接觸20℃的冷卻輥,並直接投入20℃的水槽。之後,朝長度方向於135℃延伸4.5倍,在拉幅機的寬度方向延伸中,將預熱溫度設為166℃,將延伸第1段的溫度設為155℃,將第2段的溫度設為139℃,將冷卻溫度設為95℃,將熱固定溫度設為158℃。獲得的膜的厚度為19.2μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件,於表3顯示物性。該膜的物性,如同於表3所示,係在高溫的熱收縮率較高。[Comparative example 3] As the polypropylene resin, PP-3 (FL203D, manufactured by Nippon Polypropylene Co., Ltd.) with MFR=3g/10 minutes, Tc=117.2°C, and Tm=160.6°C was used. The sheet is extruded from a T-die at 250°C, contacted with a cooling roll at 20°C, and directly put into a water tank at 20°C. Thereafter, the length direction was extended 4.5 times at 135°C. During the widthwise extension of the tenter, the preheating temperature was set to 166°C, the temperature of the first stretch step was set to 155°C, and the temperature of the second step was set to 155°C. is 139°C, the cooling temperature is set to 95°C, and the heat fixing temperature is set to 158°C. The thickness of the film obtained was 19.2 μm. Table 1 shows the structure of the polypropylene resin, Table 2 shows the film forming conditions, and Table 3 shows the physical properties. The physical properties of this film, as shown in Table 3, are that the thermal shrinkage rate at high temperatures is high.

[比較例4] 作為聚丙烯原料,是使用了MFR=2.7g/10分鐘、Tc=114.7℃、Tm=163.0℃之PP-4(住友化學股份有限公司製造,FS2012)。在250℃自T字模擠壓成片狀,使之接觸20℃的冷卻輥,並直接投入20℃的水槽。之後,朝長度方向於145℃延伸4.5倍,在拉幅機的寬度方向延伸中,將預熱溫度設為170℃,將延伸第1段的溫度設為160℃,將延伸第2段的溫度設為145℃,將冷卻溫度設為100℃,將熱固定溫度設為163℃。獲得的膜的厚度為21.2μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件,於表3顯示物性。該膜的物性,如同於表3所示,係在高溫的熱收縮率較高。[Comparative example 4] As the polypropylene raw material, PP-4 (manufactured by Sumitomo Chemical Co., Ltd., FS2012) with MFR=2.7g/10 minutes, Tc=114.7°C, and Tm=163.0°C was used. The sheet is extruded from a T-die at 250°C, contacted with a cooling roll at 20°C, and directly put into a water tank at 20°C. Then, extend the length 4.5 times at 145°C. During the width direction extension of the tenter, set the preheating temperature to 170°C, set the temperature of the first stretch step to 160°C, and set the temperature of the second stretch step to 160°C. Set to 145°C, the cooling temperature to 100°C, and the heat fixing temperature to 163°C. The thickness of the film obtained was 21.2 μm. Table 1 shows the structure of the polypropylene resin, Table 2 shows the film forming conditions, and Table 3 shows the physical properties. The physical properties of this film, as shown in Table 3, are that the thermal shrinkage rate at high temperatures is high.

[比較例5] 作為聚丙烯樹脂,是使用了PP-4。在250℃自T字模擠壓成片狀,使之接觸20℃的冷卻輥,並直接投入20℃的水槽。之後,朝長度方向在130℃延伸5.8倍後,以拉幅機將預熱溫度設為167℃來加熱膜,接著以延伸溫度161℃朝寬度方向延伸8.6倍,之後,一邊施以弛緩10%一邊在130℃進行熱固定,繼而在140℃進行第2段的熱固定。獲得的膜的厚度為13.4μm。於表1顯示聚丙烯樹脂的結構,於表2顯示製膜條件,於表3顯示物性。該膜的物性,如同於表3所示,係在高溫的熱收縮率較高。[Comparative example 5] As the polypropylene resin, PP-4 is used. The sheet is extruded from a T-die at 250°C, contacted with a cooling roll at 20°C, and directly put into a water tank at 20°C. Thereafter, after stretching 5.8 times in the length direction at 130°C, the film was heated by setting the preheating temperature to 167°C using a tenter, and then stretched 8.6 times in the width direction at a stretching temperature of 161°C. After that, it was relaxed by 10%. One side is heat-set at 130°C, and then the second step is heat-set at 140°C. The thickness of the film obtained was 13.4 μm. Table 1 shows the structure of the polypropylene resin, Table 2 shows the film forming conditions, and Table 3 shows the physical properties. The physical properties of this film, as shown in Table 3, are that the thermal shrinkage rate at high temperatures is high.

[表1]   PP-1 PP-2 PP-3 PP-4 丙烯以外之成分 共聚量(莫耳%) 0 0 0 0 MFR(g/10分鐘) 7.5 11 3 2.7 [mmmm](%) 98.9 98.8 94.8 98.7 Tc(℃) 116.2 116.5 117.2 114.7 Tm(℃) 162.5 161.5 160.6 163.0 ΔHc(J/g) 104.8 107.8 94.9 102.4 分子量1萬以下之成分量 (質量%) 4.0 6.9 3.0 3.5 分子量10萬以下之成分量 (質量%) 40.5 53.1 37.1 30.0 [Table 1] PP-1 PP-2 PP-3 PP-4 Copolymerization amount of ingredients other than propylene (mol%) 0 0 0 0 MFR (g/10 minutes) 7.5 11 3 2.7 [mmmm](%) 98.9 98.8 94.8 98.7 Tc(℃) 116.2 116.5 117.2 114.7 Tm(℃) 162.5 161.5 160.6 163.0 ΔHc(J/g) 104.8 107.8 94.9 102.4 Amount of ingredients with molecular weight less than 10,000 (mass %) 4.0 6.9 3.0 3.5 Amount of ingredients with molecular weight less than 100,000 (mass %) 40.5 53.1 37.1 30.0

[表2]   實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 比較例1 比較例2 比較例3 比較例4 比較例5 原料聚丙烯樹脂 PP-1 100 80 80 80 80 80 80 80 100 80       PP-2   20 20 20 20 20 20 20   20       PP-3                     100     PP-4                       100 100 混合聚丙烯樹脂 熔體流動速率 (g/10分鐘) 7.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 7.5 8.5 3 2.7 2.7 分子量10萬以下之成分量(質量%) 40.5 43.0 43.0 43.0 43.0 43.0 43.0 43.0 40.5 43.0 37.1 30.0 30.0 擠壓步驟 擠壓溫度(℃) 250 250 250 250 250 250 250 250 250 250 250 250 250 冷卻溫度(℃) 20 20 20 20 20 20 20 20 20 20 20 20 20 長度方向延伸步驟 長度方向延伸溫度 145 142 142 145 142 142 142 142 143 143 135 145 130 長度方向延伸倍率(倍) 4.5 4.5 4.5 4.5 4.5 4.5 4.8 4.5 4.5 4.5 4.5 4.5 5.8 預熱步驟 預熱溫度(℃) 170 170 170 170 170 170 170 170 170 170 166 170 167 寬度方向延伸步驟 前期區間寬度方向延伸溫度(℃) 160 162 162 162 162 162 162 162 158 158 155 160 161 前期區間寬度方向延伸倍率(倍) 6 6 6 6 6 6 6 6.6 6 6 6 6 6.2 後期區間寬度方向延伸溫度 145 145 145 145 145 155 145 145 158 158 139 145 161 後期區間寬度方向延伸倍率(倍) 1.36 1.36 1.36 1.36 1.36 1.36 1.36 1.5 1.36 1.36 1.36 1.36 1.39 最終寬度方向延伸倍率 8.2 8.2 8.2 8.2 8.2 8.2 8.2 9.9 8.2 8.2 8.2 8.2 8.6 寬度方向延伸結束隨後溫度(℃) 100 100 100 140 - 100 100 100 - - 95 100 - 熱處理步驟 熱處理溫度(℃) 163 165 165 165 165 165 165 165 168 168 158 163 130 熱處理時的弛緩率(%) 0 0 3 0 0 0 0 0 0 0 0 0 10 熱處理2溫度(℃) - - - - - - - - - - - - 140 [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Raw material polypropylene resin PP-1 100 80 80 80 80 80 80 80 100 80 PP-2 20 20 20 20 20 20 20 20 PP-3 100 PP-4 100 100 Hybrid polypropylene resin Melt flow rate (g/10 minutes) 7.5 8.5 8.5 8.5 8.5 8.5 8.5 8.5 7.5 8.5 3 2.7 2.7 Amount of ingredients with molecular weight less than 100,000 (mass %) 40.5 43.0 43.0 43.0 43.0 43.0 43.0 43.0 40.5 43.0 37.1 30.0 30.0 extrusion step Extrusion temperature (℃) 250 250 250 250 250 250 250 250 250 250 250 250 250 Cooling temperature(℃) 20 20 20 20 20 20 20 20 20 20 20 20 20 Lengthwise extension steps lengthwise extension temperature 145 142 142 145 142 142 142 142 143 143 135 145 130 Length direction extension ratio (times) 4.5 4.5 4.5 4.5 4.5 4.5 4.8 4.5 4.5 4.5 4.5 4.5 5.8 warm-up step Preheating temperature (℃) 170 170 170 170 170 170 170 170 170 170 166 170 167 Width direction extension steps Temperature extending in the width direction of the early period (℃) 160 162 162 162 162 162 162 162 158 158 155 160 161 Extension ratio in the width direction of the early stage interval (times) 6 6 6 6 6 6 6 6.6 6 6 6 6 6.2 Later interval width direction extension temperature 145 145 145 145 145 155 145 145 158 158 139 145 161 Post-interval width direction extension magnification (times) 1.36 1.36 1.36 1.36 1.36 1.36 1.36 1.5 1.36 1.36 1.36 1.36 1.39 Final width direction extension ratio 8.2 8.2 8.2 8.2 8.2 8.2 8.2 9.9 8.2 8.2 8.2 8.2 8.6 Temperature after end of widthwise extension (°C) 100 100 100 140 - 100 100 100 - - 95 100 - Heat treatment steps Heat treatment temperature (℃) 163 165 165 165 165 165 165 165 168 168 158 163 130 Relaxation rate during heat treatment (%) 0 0 3 0 0 0 0 0 0 0 0 0 10 Heat treatment 2 temperature (℃) - - - - - - - - - - - - 140

[表3]   實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 比較例1 比較例2 比較例3 比較例4 比較例5 膜特性 厚度(μm) 18.7 21.3 21.1 18.9 19.5 20.3 19.1 20.1 18.6 20.0 19.2 21.2 13.4 霧度(%) 0.7 2.2 2.0 2.0 2.1 2.1 2.2 2.0 1.0 1.1 0.4 0.4 0.6 23℃的F5 (寬度方向)(MPa) 193 180 169 171 183 175 184 188 133 131 158 183 210 23℃的F5 (長度方向)(MPa) 49 44 46 46 46 45 45 46 44 44 39 46 55 80℃的F5 (寬度方向)(MPa) 102 89 91 91 100 93 97 100 72 68 65 84 98 80℃的F5 (長度方向)(MPa) 21 21 21 20 21 22 21 21 20 20 13 18 23 23℃的楊氏模數 (寬度方向)(GPa) 7.4 7.1 6.7 6.7 6.9 6.9 7.1 7.3 5.5 5.7 6.1 7.1 7.7 23℃的楊氏模數 (長度方向)(GPa) 2.7 2.5 2.5 2.6 2.5 2.6 2.5 2.6 2.7 2.6 2.4 2.6 2.9 80℃的楊氏模數 (寬度方向)(GPa) 3.3 3.0 3.0 3.0 3.2 3.0 3.2 3.2 2.2 2.0 2.1 2.9 3.4 80℃的楊氏模數 (長度方向)(GPa) 0.8 1.0 1.0 0.9 1.0 1.0 0.9 1.0 0.9 0.9 0.6 0.6 0.9 拉伸斷裂強度 (寬度方向)(MPa) 450 397 366 396 435 373 379 391 336 344 414 430 476 拉伸斷裂強度 (長度方向)(MPa) 134 106 105 111 114 106 117 113 118 124 163 160 182 拉伸斷裂伸度 (寬度方向)(%) 27 26 22 32 29 24 21 22 37 44 29 27 33 拉伸斷裂伸度 (長度方向)(%) 178 176 172 179 199 182 173 190 188 219 201 192 160 TMA(寬度方向)(μm) 25 13 18 11 11 34 21 23 222 198 13 6 18 TMA(長度方向)(μm) 1366 1551 1189 1335 1487 1724 1304 1361 1574 1487 2422 1629 2411 120℃熱收縮率 (寬度方向)(%) 4.0 3.0 2.2 3.0 3.0 3.3 3.0 2.7 0.7 1.0 9.8 6.5 2.7 120℃熱收縮率 (長度方向)(%) 1.0 1.0 1.0 0.8 1.0 1.0 1.0 0.8 1.3 1.3 4.0 1.7 1.5 150℃熱收縮率 (寬度方向)(%) 27.3 22.0 18.2 17.8 24.7 18.3 17.7 17.3 11.7 13.2 57.0 43.0 37.8 150℃熱收縮率 (長度方向)(%) 7.0 5.0 4.2 5.2 5.3 5.8 3.5 4.3 4.7 4.3 34.0 17.0 13.7 寬度方向折射率Ny 1.5245 1.5254 1.5258 1.5250 1.5261 1.5260 1.5249 1.5259 1.5252 1.5245 1.5187 1.5215 1.5251 長度方向折射率Nx 1.5020 1.5028 1.5034 1.5030 1.5020 1.5031 1.5031 1.5020 1.5050 1.5056 1.4991 1.5010 1.4997 厚度方向折射率Nz 1.4985 1.5001 1.5001 1.5000 1.4997 1.5007 1.4998 1.4999 1.5012 1.5010 1.4952 1.4973 1.4980 ΔNy 0.0243 0.0240 0.0240 0.0235 0.0253 0.0241 0.0234 0.0250 0.0221 0.0212 0.0216 0.0224 0.0262 面配向係數ΔP 0.0148 0.0140 0.0145 0.0140 0.0144 0.0139 0.0142 0.0141 0.0139 0.0141 0.0137 0.0140 0.0144 X射線半值寬度(°) 20.6 22.2 23.0 23.8 20.2 23.6 23.6 21.8 28.6 28.9 23.9 24.4 21.2 X射線配向度 0.89 0.88 0.87 0.87 0.89 0.87 0.87 0.88 0.84 0.84 0.87 0.86 0.88 彎曲剛度(寬度方向) (mN・cm) 0.60 0.68 0.71 0.70 0.56 0.67 0.60 0.61 0.42 0.50 0.82 0.72 0.36 彎曲剛度(長度方向) (mN・cm) 0.34 0.37 0.39 0.39 0.36 0.35 0.33 0.36 0.31 0.34 0.43 0.35 0.24 環剛度斜率a (寬度方向) 0.00114 0.00120 0.00117 0.00113 0.00120 0.00117 0.00116 0.00127 0.00112 0.00109 0.00087 0.00087 0.00138 環剛度斜率a (長度方向) 0.00038 0.00048 0.00049 0.00046 0.00044 0.00045 0.00046 0.00046 0.00052 0.00050 0.00035 0.00035 0.00059 [table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Membrane properties Thickness(μm) 18.7 21.3 21.1 18.9 19.5 20.3 19.1 20.1 18.6 20.0 19.2 21.2 13.4 Haze(%) 0.7 2.2 2.0 2.0 2.1 2.1 2.2 2.0 1.0 1.1 0.4 0.4 0.6 F5 (width direction) at 23℃(MPa) 193 180 169 171 183 175 184 188 133 131 158 183 210 F5 (length direction) at 23℃(MPa) 49 44 46 46 46 45 45 46 44 44 39 46 55 F5 (width direction) at 80℃(MPa) 102 89 91 91 100 93 97 100 72 68 65 84 98 F5 (length direction) at 80℃(MPa) twenty one twenty one twenty one 20 twenty one twenty two twenty one twenty one 20 20 13 18 twenty three Young's modulus (width direction) at 23°C (GPa) 7.4 7.1 6.7 6.7 6.9 6.9 7.1 7.3 5.5 5.7 6.1 7.1 7.7 Young's modulus (length direction) at 23°C (GPa) 2.7 2.5 2.5 2.6 2.5 2.6 2.5 2.6 2.7 2.6 2.4 2.6 2.9 Young's modulus (width direction) at 80°C (GPa) 3.3 3.0 3.0 3.0 3.2 3.0 3.2 3.2 2.2 2.0 2.1 2.9 3.4 Young's modulus (length direction) at 80°C (GPa) 0.8 1.0 1.0 0.9 1.0 1.0 0.9 1.0 0.9 0.9 0.6 0.6 0.9 Tensile breaking strength (width direction) (MPa) 450 397 366 396 435 373 379 391 336 344 414 430 476 Tensile breaking strength (length direction) (MPa) 134 106 105 111 114 106 117 113 118 124 163 160 182 Tensile elongation at break (width direction) (%) 27 26 twenty two 32 29 twenty four twenty one twenty two 37 44 29 27 33 Tensile elongation at break (length direction) (%) 178 176 172 179 199 182 173 190 188 219 201 192 160 TMA (width direction) (μm) 25 13 18 11 11 34 twenty one twenty three 222 198 13 6 18 TMA (length direction) (μm) 1366 1551 1189 1335 1487 1724 1304 1361 1574 1487 2422 1629 2411 Thermal shrinkage rate at 120℃ (width direction) (%) 4.0 3.0 2.2 3.0 3.0 3.3 3.0 2.7 0.7 1.0 9.8 6.5 2.7 Thermal shrinkage rate at 120℃ (length direction) (%) 1.0 1.0 1.0 0.8 1.0 1.0 1.0 0.8 1.3 1.3 4.0 1.7 1.5 Thermal shrinkage rate at 150℃ (width direction) (%) 27.3 22.0 18.2 17.8 24.7 18.3 17.7 17.3 11.7 13.2 57.0 43.0 37.8 Thermal shrinkage rate at 150℃ (length direction) (%) 7.0 5.0 4.2 5.2 5.3 5.8 3.5 4.3 4.7 4.3 34.0 17.0 13.7 Width direction refractive index Ny 1.5245 1.5254 1.5258 1.5250 1.5261 1.5260 1.5249 1.5259 1.5252 1.5245 1.5187 1.5215 1.5251 Longitudinal refractive index Nx 1.5020 1.5028 1.5034 1.5030 1.5020 1.5031 1.5031 1.5020 1.5050 1.5056 1.4991 1.5010 1.4997 Thickness direction refractive index Nz 1.4985 1.5001 1.5001 1.5000 1.4997 1.5007 1.4998 1.4999 1.5012 1.5010 1.4952 1.4973 1.4980 ΔNy 0.0243 0.0240 0.0240 0.0235 0.0253 0.0241 0.0234 0.0250 0.0221 0.0212 0.0216 0.0224 0.0262 Plane alignment coefficient ΔP 0.0148 0.0140 0.0145 0.0140 0.0144 0.0139 0.0142 0.0141 0.0139 0.0141 0.0137 0.0140 0.0144 X-ray half value width (°) 20.6 22.2 23.0 23.8 20.2 23.6 23.6 21.8 28.6 28.9 23.9 24.4 21.2 X-ray alignment degree 0.89 0.88 0.87 0.87 0.89 0.87 0.87 0.88 0.84 0.84 0.87 0.86 0.88 Bending stiffness (width direction) (mN・cm) 0.60 0.68 0.71 0.70 0.56 0.67 0.60 0.61 0.42 0.50 0.82 0.72 0.36 Bending stiffness (length direction) (mN・cm) 0.34 0.37 0.39 0.39 0.36 0.35 0.33 0.36 0.31 0.34 0.43 0.35 0.24 Ring stiffness slope a (width direction) 0.00114 0.00120 0.00117 0.00113 0.00120 0.00117 0.00116 0.00127 0.00112 0.00109 0.00087 0.00087 0.00138 Ring stiffness slope a (length direction) 0.00038 0.00048 0.00049 0.00046 0.00044 0.00045 0.00046 0.00046 0.00052 0.00050 0.00035 0.00035 0.00059

Claims (9)

一種雙軸配向聚丙烯膜,係以熱機械分析裝置(TMA)所測定於150℃以下的最大伸長量在長度方向為1.5mm以下,在寬度方向為0.1mm以下,且於150℃中的熱收縮率在長度方向為10%以下,在寬度方向為30%以下;前述最大伸長量係使用島津製作所製造的熱機械分析裝置TMA-60,以夾具間隔10mm設置寬度4mm的膜樣品,並以測定荷重40g且以20℃/分鐘自30℃昇溫至180℃來測定至150℃為止的最大伸長量。 A biaxially aligned polypropylene film with a maximum elongation of 1.5 mm or less in the length direction and 0.1 mm or less in the width direction measured at 150°C or less by a thermomechanical analysis device (TMA), and the thermal stress at 150°C The shrinkage rate is 10% or less in the length direction and 30% or less in the width direction; the aforementioned maximum elongation is measured using a thermomechanical analysis device TMA-60 manufactured by Shimadzu Corporation, with a film sample of 4 mm width set at a clamp interval of 10 mm. A load of 40 g was applied and the temperature was increased from 30°C to 180°C at 20°C/min to measure the maximum elongation to 150°C. 如請求項1所記載的雙軸配向聚丙烯膜,其中前述雙軸配向聚丙烯膜之120℃熱收縮率在長度方向為2.0%以下,在寬度方向為5.0%以下,且長度方向的120℃熱收縮率小於寬度方向的120℃熱收縮率。 The biaxially aligned polypropylene film as described in claim 1, wherein the 120°C thermal shrinkage rate of the biaxially aligned polypropylene film is 2.0% or less in the length direction, 5.0% or less in the width direction, and the 120°C thermal shrinkage rate in the length direction is 2.0% or less. The thermal shrinkage rate is less than the 120°C thermal shrinkage rate in the width direction. 如請求項1或2所記載的雙軸配向聚丙烯膜,其中前述雙軸配向聚丙烯膜的寬度方向之折射率Ny為1.5230以上,△Ny為0.0220以上。 The biaxially aligned polypropylene film according to claim 1 or 2, wherein the refractive index Ny in the width direction of the biaxially aligned polypropylene film is 1.5230 or more, and ΔNy is 0.0220 or more. 如請求項1或2所記載的雙軸配向聚丙烯膜,其中前述雙軸配向聚丙烯膜的霧度為5.0%以下。 The biaxially aligned polypropylene film according to claim 1 or 2, wherein the haze of the biaxially aligned polypropylene film is 5.0% or less. 如請求項1或2所記載的雙軸配向聚丙烯膜,其中構成前述雙軸配向聚丙烯膜的聚丙烯樹脂之內消旋五單元組分率為97.0%以上。 The biaxially aligned polypropylene film according to claim 1 or 2, wherein the polypropylene resin constituting the biaxially aligned polypropylene film has a meso pentad component ratio of 97.0% or more. 如請求項1或2所記載的雙軸配向聚丙烯膜,其中構成前述雙軸配向聚丙烯膜的聚丙烯樹脂之結晶化溫度為105℃以上,熔點為160℃以上。 The biaxially aligned polypropylene film according to claim 1 or 2, wherein the polypropylene resin constituting the biaxially aligned polypropylene film has a crystallization temperature of 105°C or higher and a melting point of 160°C or higher. 如請求項1或2所記載的雙軸配向聚丙烯膜,其中構成前述雙軸配向聚丙烯膜的聚丙烯樹脂之熔體流動速率為4.0g/10分鐘以上。 The biaxially aligned polypropylene film according to claim 1 or 2, wherein the polypropylene resin constituting the biaxially aligned polypropylene film has a melt flow rate of 4.0 g/10 minutes or more. 如請求項1或2所記載的雙軸配向聚丙烯膜,其中構成前述雙軸配向聚丙烯膜的聚丙烯樹脂之分子量10萬以下的成分量為35質量%以上。 The biaxially aligned polypropylene film according to claim 1 or 2, wherein the component amount of the polypropylene resin constituting the biaxially aligned polypropylene film having a molecular weight of 100,000 or less is 35 mass % or more. 如請求項1或2所記載的雙軸配向聚丙烯膜,其中前述雙軸配向聚丙烯膜的配向度為0.85以上。 The biaxially aligned polypropylene film according to claim 1 or 2, wherein the alignment degree of the biaxially aligned polypropylene film is 0.85 or more.
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